Beyond Isolated-Molecule TDDFT: Solvation, Aggregation, and Interfacial Fields in Predicting Spectroscopic Signatures and Charge-Transfer Mechanisms – A Systematic Review

Beyond Isolated-Molecule TDDFT: Solvation, Aggregation, and Interfacial Fields in Predicting Spectroscopic Signatures and Charge-Transfer Mechanisms – A Systematic Review | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Beyond Isolated-Molecule TDDFT: Solvation, Aggregation, and Interfacial Fields in Predicting Spectroscopic Signatures and Charge-Transfer Mechanisms – A Systematic Review Frans Augusthinus Asmuruf, Yohanis Irenius Mandik, Yuliana Ruth Yabansabra, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8815313/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Density functional theory and time-dependent density functional theory are commonly used to interpret and predict spectroscopic properties of molecular and materials systems. However, a significant portion of TDDFT-based spectroscopic investigations still use isolated-molecule approximations that cannot reproduce the decisive role that realistic environments often play. In this comprehensive literature review, we recapitulate recent advances in environment-resolved DFT/TDDFT spectroscopy, with particular focus on the contributions of solvation, molecular aggregation, and interfacial electric fields to spectral signatures and charge-transfer mechanisms. In accordance with a PRISMA-style review design, the analysis of 83 peer-reviewed studies generated from all major application areas (such as molecular chromophores, fluorescent sensors, photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces). The findings emphasize that environmental interactions are not secondary perturbations but profoundly influence the excited-state electronic structure, often leading to qualitative changes in spectral features and mechanistic insights. Key studies in the surveyed literature consistently indicate that explicit microsolvation, aggregation modeling, and interface- and field-resolved methods improve spectroscopic fidelity to isolated-molecule models. This review lays out a comprehensive framework for environment-resolved computational spectroscopy and highlights many methodological gaps, e.g., disparate validation and the lack of consideration of collective and interfacial effects. In this paper, we aim to advance DFT/TDDFT spectroscopy toward predictive reliability and quantitative accuracy for complex molecular and materials systems by outlining best-practice recommendations and future research directions. Density functional theory (DFT) Time-dependent density functional theory (TDDFT) Computational spectroscopy Systematic literature review Figures Figure 1 Figure 2 Figure 3 Figure 4 1. Introduction Density functional theory (DFT) and time-dependent density functional theory (TDDFT) are nowadays essential methods in contemporary computational chemistry to understand and predict spectroscopic properties of molecular and materials systems [ 1 – 3 ]. In the last decades, TDDFT has been increasingly used to simulate electronic absorption and emission spectra, excited-state processes, and charge transfer in diverse chemical settings [ 2 – 5 ], ranging from molecular chromophores to fluorescent sensors, active photo-materials, and hybrid interfaces. Because TDDFT offers a good compromise between efficient calculations and satisfactory accuracy, it is increasingly used as a complement to experimental spectroscopy. Despite their striking success, TDDFT-based spectral simulations still rely on isolated-molecule descriptions, with only rough simplifications of their immediate environment (e.g., an implicit dielectric model) [ 6 , 7 ]. In such schemes, molecules are treated as independent, all-electron particles, and the environment is included only through homogeneous screening. Although such methods may be adequate for the qualitative interpretation of results in weakly interacting systems, they are now recognized as inadequate for excited states that display large charge-transfer character [ 8 – 10 ], strong polarization, or sensitivity to local structural ordering. It is acknowledged that, in realistic chemical environments, the spectroscopic fingerprints are seldom due solely to intrinsic molecular features. On the contrary, solvation structure, molecular aggregation, and interfacial electric field are often crucial in determining excited-state potential energy surfaces, transition density, and oscillator strength [ 11 – 14 ]. There is a large body of computational and experimental work supporting the idea that explicit solute–solvent effects can significantly shift excitation and emission energies, modify excited-state orderings, and reassign mechanisms in photoinduced processes such as intramolecular charge transfer or periodic reactions [ 15 – 18 ]. Aggregation or packing effects in condensed phases can similarly introduce collective excited states that are absent from single-molecule descriptions and dominate observed spectroscopic responses [ 19 – 22 ]. These restrictions are especially pronounced in systems in which spectroscopy directly correlates with function. In the case of fluorescent and sensing probes, the solvating and coordinating environment has been shown to directly control sensitivity and selectivity [ 23 – 25 ]. Aggregation-induced electronic coupling and interfacial polarization in photoactive materials for optoelectronics and energy conversion govern the onset of absorption and emission pathways and charge-separation efficiency [ 26 – 28 ]. At hybrid interfaces between dyes and semiconductors, or in perovskite-based heterostructures, local electric fields and electronic alignment can radically alter charge-transfer properties and spectroscopic signatures [ 13 , 30 – 32 ]. In this situation, spectroscopic predictions made using TDDFT models of isolated molecules are likely to give an incomplete or incorrect physical picture. These findings reveal fundamental conceptual and computational insufficiencies of the isolated-molecule TDDFT formalism. In many of the current systems of interest, such as thermally activated delayed fluorescence (TADFs) emitters, metal-organic frameworks, nanoclusters, and interfacial assemblies [ 19 , 20 , 26 , 33 ], spectral features arise from environment-mediated electronic interactions rather than from isolated chromophores. Hence, the view that environmental degrees of freedom are not simply perturbations but must be considered as part of, and integrated into, the electronic-structure problem is becoming increasingly widespread. In addressing these challenges, a methodological transition has been made in recent years toward environmentally resolved computational spectroscopy: a hierarchy of modeling methods, from coarse-grained to all-atom, for the molecules of interest [ 7 , 11 , 14 ]. These strategies cover implicit solvation models, explicit microsolvation, aggregation and packing models, and interface- or field-resolved approaches. Although these approaches have proven beneficial across a range of studies, their application has been partial; no consistent recommendation exists on the desirable minimum level of habitat heterogeneity and its nature (i.e., whether it should be added in an artificial form or as reintroduced natural elements) [ 12 , 16 , 29 ]. Figure 1. Conceptual framework illustrating hierarchical modeling strategies in DFT/TDDFT-based computational spectroscopy. The framework progresses from isolated-molecule calculations to increasingly environment-resolved approaches, including implicit solvation, explicit microsolvation, aggregation or packing models, and interface and field-resolved representations. As environmental realism increases, spectroscopic predictions more accurately capture charge-transfer character, polarization effects, and experimentally observed spectral signatures. The conceptual framework of this review is depicted in Fig. 1, emphasizing the continuum from isolated-molecule TDDFT to increasingly environment-defined spectral modeling. Schematically, the incorporation of solvation, aggregation, and interfacial effects also gives rise to additional electronic interactions that significantly alter excited-state properties and spectroscopic fingerprints, calling for environment-adaptive computational tools (48). In this light, a comprehensive compilation of the field of environment-aware DFT/TDDFT spectroscopy is due and timely. The existing reviews typically focus solely on methodological advances in TDDFT or on specific application fields, without placing solvation, aggregation, and interfacial effects as a unified theoretical concept clearly at the core [ 1 , 5 , 8 ]. As a result, the broader relevance of environmental effects for spectroscopic modeling and their interplay with intrinsic limitations of TDDFT are not well articulated. In this contribution, we review the literature on spectroscopic studies using DFT and TD-DFT, with particular emphasis on environmental effects. In this review, we adopt a PRISMA-like review design [ 34 – 35 ] to assess a wide range of recent literature on molecular chromophores, sensors, and photoactive materials, as well as supramolecular assemblies, nanoclusters, and hybrid interfaces. This review has three main goals: (i) to survey application domains and modeling approaches that dominate in environment-aware computational spectroscopy, (ii) to critically evaluate how solvation, aggregation , or interfacial fields can affect both spectroscopic signatures and charge-transfer mechanisms, and (iii) to point out methodological/interpretative shortcomings as well as advice for best-practice decisions. The purpose of such an accumulation is to provide context and perspective, consolidating knowledge across diverse systems to broaden what remain largely case-specific methodologies into a more coherent and predictive modeling paradigm for environment-resolved TDDFT spectroscopy. 2. Methods 2.1. Review Design and Reporting Framework This study was conducted as a systematic literature review (SLR) following the principles and reporting standards of the PRISMA 2020 guidelines [ 34 – 35 ]. The PRISMA framework was adopted to ensure transparency, reproducibility, and methodological rigor in the identification, screening, eligibility assessment, and inclusion of relevant studies. A PRISMA-based workflow was implemented to define the scope of the review, minimize selection bias, and provide a clear audit trail of the study selection process. The overall review design and study selection process are summarized in the PRISMA flow diagram shown in Fig. 2 . The diagram provides a transparent overview of the identification, screening, eligibility assessment, and final inclusion of studies analyzed in this review, ensuring methodological rigor and reproducibility in accordance with the PRISMA 2020 guidelines. 2.2. Literature Search Strategy A structured and comprehensive literature search was performed across major scientific databases, including Web of Science and Scopus, which collectively provide broad coverage of journals in computational chemistry, spectroscopy, and materials science. Additional records were identified through publisher platforms associated with Springer Nature, Elsevier, ACS Publications, and the Nature Portfolio. Search queries were constructed using combinations of methodological and application-oriented keywords to capture studies employing DFT or TDDFT for spectroscopic analysis. Representative search strings included: DFT” OR “TDDFT” AND “spectroscopy "time-dependent density functional theory" AND "UV–Vis" OR "fluorescence" "TDDFT" AND "charge transfer" AND ("solvation" OR "aggregation" OR "interface"). The search strategy was iteratively refined to balance sensitivity and specificity, following best practices for systematic reviews in computational and interdisciplinary research [ 36 ]. 2.3. Inclusion and Exclusion Criteria The inclusion criteria were developed in advance to promote uniformity and the usefulness of applied content. Inclusion criteria were: Original peer-reviewed research articles. Use of the DFT and/or TDDFT. Emphasis on spectroscopic properties (i.e., electronic absorption, emission, vibrational, electroabsorption, or X-ray spectroscopies). Excited states, charge-transfer processes, or spectroscopic signatures of interest for either molecular or materials systems. Exclusion criteria were: Review articles, perspectives, or editorials. Studies lacking a spectroscopic component. Methodological developments only; not applied to spectral interpretation. Articles with inadequate methodological information for the assessment of computational reliability. These inclusion and exclusion criteria are maintained throughout record screening and eligibility assessment. 2.4. Screening and Study Selection All relevant information from database searches was imported in the first round, and duplicates were filtered out. The titles and abstracts were reviewed in order to discard those studies that could be easily assumed not to fall within the field of DFT/TDDFT-based spectroscopy. Full-text screening was then conducted to assess eligibility according to the predetermined inclusion and exclusion criteria. The last set of retained studies comprises the sample we analyzed in Section 3 and will serve as the source of evidence for our descriptive mapping (Section 3 ) and thematic synthesis (Section 4 ). The selection of studies is clearly noted in the PRISMA flow diagram presented in Fig. 2 . 2.5. Data Extraction and Classification For each included study, structured data extraction was carried out using a predefined extraction matrix corresponding to Supplementary Table S1 (Master SLR Table). Extracted information included bibliographic details, application domain, spectroscopic modality, computational methodology (DFT, TDDFT, or variants), and the treatment of environmental effects. To enable cross-study comparison, each article was classified according to: Application domain, following the taxonomy summarized in Fig. 3 (e.g., molecular chromophores, sensors, photoactive materials, supramolecular assemblies, nanoclusters, and interfaces). Environmental treatment, including gas-phase or isolated-molecule models, implicit solvation, explicit microsolvation, aggregation or packing models, and interface- or field-resolved approaches. Analytical role, distinguishing between core thematic studies and supporting studies , as summarized in Supplementary Table S2 . 2.6. Quality Appraisal Methodological quality was assessed qualitatively rather than through numerical scoring, in line with recommendations for systematic reviews involving heterogeneous computational methodologies [ 28 , 36 – 37 ]. The appraisal focused on the transparency of computational details, the adequacy of environmental modeling, validation against experimental data or higher-level theoretical methods, and the consistency of spectroscopic assignments. Studies were not excluded solely based on methodological limitations; instead, quality considerations informed the weighting of evidence during thematic synthesis. 2.7. Synthesis Strategy Given the diversity of systems, spectroscopic techniques, and computational strategies represented in the reviewed literature, a narrative thematic synthesis approach was adopted [ 38 – 39 ]. This approach emphasizes identifying recurring mechanistic patterns, methodological trends, and research gaps rather than quantitative aggregation. The synthesis integrates evidence across application domains to elucidate how solvation, aggregation, and interfacial effects systematically influence spectroscopic signatures and charge-transfer mechanisms in DFT/TDDFT-based studies. 3. Results 3.1. Overview of the Reviewed Corpus Following the eligibility assessment, 92 peer-reviewed articles met the inclusion criteria (Fig. 2 ). Of these, 83 studies formed the final analytical corpus for thematic synthesis, while the remaining studies were retained as contextual or supporting references and not included in the core thematic analysis. These studies span a broad temporal range, with a clear concentration in the last five to seven years, reflecting growing interest in environment-aware spectroscopic modeling using DFT and TDDFT. The reviewed literature encompasses a diverse set of molecular and materials systems, spectroscopic techniques, and computational strategies, underscoring the methodological and application-driven heterogeneity of the field. Across the corpus, TDDFT emerges as the dominant computational approach for modeling electronic absorption and emission spectra, frequently complemented by ground-state DFT calculations for structural optimization and electronic analysis. Variants such as the Tamm–Dancoff approximation (TDA), long-range corrected functionals, and hybrid exchange–correlation schemes are commonly employed to mitigate known deficiencies of conventional TDDFT, particularly in systems with significant charge-transfer character [ 8 – 9 , 10 , 26 ]. The search strategy was iteratively refined to balance sensitivity and specificity, following best practices for systematic reviews in computational and interdisciplinary research [ 39 – 40 ]. To provide an integrated overview of the reviewed literature, Fig. 3 maps the major application domains addressed by DFT/TDDFT-based spectroscopic studies. The figure highlights the diversity of systems investigated, ranging from molecular chromophores and fluorescent sensors to photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces, while also illustrating shared methodological challenges across domains. 3.2. Dominant Application Domains Analysis of the reviewed studies reveals six major application domains, as summarized schematically in Fig. 3 . Molecular Chromophores and Excited-State Processes A substantial portion of the literature focuses on molecular chromophores exhibiting intramolecular charge transfer, excited-state proton transfer, or solvatochromic behavior. In these studies, TDDFT is used to assign electronic transitions, rationalize spectral shifts, and elucidate excited-state relaxation pathways [ 11 , 15 – 18 ]. Environmental effects are frequently invoked to explain discrepancies between gas-phase calculations and experimental spectra, particularly in polar solvents. Fluorescent Sensors and Analytical Spectroscopy Another prominent application domain involves fluorescent and chemosensory systems designed for chemical or biological detection. Here, spectroscopic responses are often highly sensitive to solvation, coordination, and local electrostatic environments. TDDFT-based studies in this domain commonly incorporate implicit or explicit solvation models to rationalize emission shifts, fluorescence quenching, or enhancement mechanisms [ 23 – 25 ]. Photoactive Materials for Energy Conversion Photoactive materials, including organic photovoltaics, dye-sensitized systems, and light-emitting materials, constitute a third major domain. In these systems, aggregation-induced electronic coupling and interfacial effects play central roles in determining absorption onsets and charge-separation efficiencies. The reviewed studies highlight the need to model intermolecular interactions and interfaces to capture experimentally observed spectroscopic trends [ 26 – 29 ]. Supramolecular Assemblies and Metal–Organic Frameworks Several studies address supramolecular assemblies and metal–organic frameworks, where collective electronic effects and host–guest interactions dominate spectroscopic behavior. TDDFT calculations in these systems frequently move beyond isolated-molecule models to include cluster or periodic representations, enabling more accurate interpretation of experimental spectra [ 19 , 20 , 33 ]. Nanoclusters and Finite-Size Systems Nanoclusters and finite-size systems represent another growing application area. In these studies, size-dependent electronic structure, surface effects, and environmental interactions are critical for understanding spectroscopic signatures. The reviewed literature demonstrates that environmental modeling is essential for capturing the interplay between quantum confinement and external perturbations [ 22 , 26 ]. Advanced Spectroscopic Modalities and Hybrid Interfaces A smaller but increasingly significant subset of studies explores advanced spectroscopic techniques, such as electroabsorption and X-ray spectroscopies, as well as hybrid interfaces involving metals, semiconductors, or electrodes. These systems often require explicit treatment of interfacial fields and electronic coupling to reproduce experimental observables [ 13 , 30 – 32 ]. 3.3. Treatment of Environmental Effects Across all application domains, the reviewed studies employ a range of strategies to incorporate environmental effects into DFT/TDDFT calculations. Isolated-Molecule and Implicit Solvation Models Isolated-molecule models, with or without implicit solvation, remain widely used due to their computational efficiency. Implicit solvation models, such as polarizable continuum approaches, are often sufficient to reproduce general solvatochromic trends but frequently fail to capture specific solute–environment interactions or state-specific polarization effects [ 8 , 9 , 13 ]. Explicit Microsolvation and Cluster Models Explicit microsolvation approaches, in which solvent molecules or coordinating species are explicitly included within the quantum-mechanical region, are increasingly adopted to capture hydrogen bonding, directional interactions, and local structural effects. Studies employing these models report improved agreement with experimental spectra and more reliable mechanistic interpretations, particularly for charge-transfer and proton-transfer processes [ 15 – 18 ]. Aggregation and Packing Effects Aggregation effects are commonly modeled using dimeric, oligomeric, or cluster representations. These approaches reveal the emergence of collective excited states and excitonic coupling that are absent in isolated-molecule calculations. The reviewed literature indicates that aggregation-induced spectral shifts and intensity changes are often dominant in condensed-phase systems [ 19 – 22 ]. Interface- and Field-Resolved Approaches For hybrid interfaces and electroactive systems, explicit modeling of interfaces or external fields is required to capture charge-transfer energetics and spectroscopic responses. Although computationally demanding, such approaches provide critical insights into systems in which interfacial polarization and electronic alignment dictate function [ 13 , 30 – 32 ]. 3.4. Methodological Trends and Validation Practices Methodological analysis of the reviewed corpus reveals an increasing use of long-range-corrected functionals and benchmarking against experimental spectra. However, validation practices remain inconsistent across studies. While some works report quantitative agreement with experimental excitation energies or spectral shapes, others rely primarily on qualitative comparisons. This variability highlights the need for standardized validation protocols in environment-resolved spectroscopic modeling [ 8 , 12 , 29 ]. 3.5. Classification of Core and Supporting Studies To facilitate focused thematic synthesis, the reviewed studies were classified according to their analytical role. Core thematic studies explicitly compare isolated-molecule and environment-resolved models and demonstrate qualitative changes in spectroscopic signatures or charge-transfer mechanisms. Supporting studies, while methodologically relevant, primarily report incremental improvements or apply established approaches without systematic comparison. This classification, summarized in Supplementary Table S2 , underpins the thematic discussion presented in Section 4 and ensures transparency in the selection of evidence used for in-depth analysis. 4. Discussion 4.1. Reinterpreting Computational Spectroscopy Outside Isolated Molecules Although isolated-molecule TDDFT has historically been a useful starting point for spectroscopic modeling, the evidence presented in this review indicates that it no longer provides an adequate approximation for modern target systems. In several application areas, spectroscopic features and charge-transfer mechanisms are observed to arise from environment-mediated electronic interactions rather than from intrinsic molecular properties alone [ 11 – 12 , 14 , 19 – 22 ]. The analysed thematic core studies all confirm that ignoring environmental freedoms of motion can lead to quantitative errors and incorrect causal interpretations. This observation motivates a paradigm shift in how we think about computational spectroscopy, in which solvation, aggregation, and interfacial effects are considered part of the electronic-structure problem. Within this context-specific picture, TDDFT calculations are no longer viewed as stand-alone measurements of a molecular property, but rather as OCAs whose predictive ability is evaluated by their success or failure in simple, operational representations of environmental complexity [ 7 , 12 , 29 ]. 4.2. Solvation at the Active Site: An Essential Factor for Excited State Geometry Solvation effects are the most studied type of environmental impact in TDDFT spectroscopy. The literature reviewed here has demonstrated that solvation plays a role that goes far beyond simply uniformly stabilizing excited states; it actually modifies transition densities and state ordering while fostering charge localization, particularly in systems with strong ICT or PT character [ 15 – 18 ]. Implicit solvation schemes model nonspecific dielectric stabilization and often qualitatively predict the correct solvatochromic trend [ 6 – 7 ]. However, the core theme studies clearly indicate that these models often do not accurately portray state-dependent polarisation and directionality of solute–solvent interactions. Pure solvent or macroscopic polar environment models typically require empirical optimization of reorganization modes. However, explicit microsolvation methodologies directly account for hydrogen bonding and local coordination, yielding better agreement with experimental measurements and greater chemical validity [ 15 – 18 ]. These results indicate that solvation is more than an energy correction: in fact, it must be considered a structural and electronic modifier. 4.3. Gatherings and Collective Excitations in Condensed Matter The second principal axis along which the isolated-molecule TDDFT error can be decomposed is aggregation and packing effects. In the complex condensed-phase environment, excitonic coupling, electronic-state delocalization, and symmetry breaking lead to collective excited states that do not appear in single-molecule descriptions [ 19 – 22 ]. The analyzed works show that aggregation-induced spectral shifts, intensity redistribution, and band broadening are often observed in the spectroscopic response. Note that aggregation effects are not particular to crystalline or highly ordered systems. Even modestly bound dimers and other short-lived clusters can lead to qualitative alterations in the nature and selection rules of excited states. Dimeric or higher-oligomeric models are thus often the simplest required step beyond isolated molecules for qualitative spectroscopic analysis [ 19 – 20 , 22 ]. These results highlight that aggregation is a general property of condensed-phase spectroscopy and not a system-specific artefact. Figure 4 schematically illustrates the trade-offs between environmental complexity, computational cost, and spectroscopic fidelity that emerge when moving beyond isolated-molecule TDDFT models. The theoretical areas where simplified models offer little physical insight, as well as those in which greater environmental fidelity leads to significant mechanistic advances but at higher computational cost, are addressed in the figure. These areas identify important methodological gaps and guide best-practice considerations in future environment-resolved TDDFT research. Figure 4. Schematic representation of the relationship between environmental complexity, computational cost, and spectroscopic reliability in DFT/TDDFT-based studies. Implicit solvation models offer low computational cost but limited accuracy for charge-transfer-dominated systems, whereas microsolvation, aggregation, and interface-resolved approaches provide enhanced spectroscopic fidelity at increased computational expense. Regions highlighted as having methodological gaps indicate where improved modeling strategies and standardization are most needed. 4.4. Interfacial fields and interfacial charge-transfer at hybrid interfaces Hybrid interfaces introduce yet another layer of complexity due to local electric fields, electronic coupling, and energy-level alignment. The literature on dye–semiconductor assemblies, metal–molecule interfaces, and electroactive systems has documented that interfacial effects can drastically alter charge-transfer routes and spectroscopic signatures [ 13 , 30 – 32 ]. Explicit results show that field-induced polarization and interfacial coupling profoundly influence excitation energies, oscillator strengths, and charge-separation efficiencies, beyond the range of gas-phase or bulk-solvation models. Although computationally intensive, explicit interface- or field-resolved models offer fundamental insight into systems that rely on interfacial behavior to function. These results emphasize that interfaces are unique spectroscopic environments that necessitate model strategies specifically designed for them, rather than extensions of solution-phase methods. 4.5. Methodological Limitations of TDDFT within Environment-Resolved Frameworks The inclusion of the environment in TDDFT responses reveals additional intrinsic limitations of the theory. Even with explicit inclusion of environmental complexity [ 8 – 10 ], charge-transfer states, long-range polarization , and collective excitations push beyond what is treatable by usual exchange–correlation functionals. The present review demonstrates that both long-range corrected functionals and TDA-based approaches can alleviate (though not fully correct) these problems. Also, the advantages of environment-resolved modeling depend strongly on the electronic-structure method used. Adding realism to the environment without restoring function becomes less and less rewarding; increasing methodological muscle in a monochromatic environment is still inadequate. It underscores the need for co-designing electronic-structure methods and environmental models for future spectroscopy studies. 4.6. Validation Methods and the Requirement for Standardization The absence of standardized validation benchmarks is a common theme throughout the literature reviewed. A few refactorings in our set have been reported to sh ow quantitative agreement with experimental spectra or to serve as benchmark cases against higher-level ab initio methods, rather than merely qualitative correspondence [ 12 , 29 ]. Such heterogeneity hinders between-studies comparisons and reduces the field’s joint predictive strength (Hauner and Meier, 2003). Recommendation: Good practice from the core thematic studies was to explicitly report on the environmental model construct, use ensemble sampling where applicable, and provide quantitative error metrics for spectral comparison. Such a practice would greatly improve the reproducibility and interpretation of environment-resolved TDDFT spectroscopies. 4.7. Research Gaps and Future Directions However, there are still some research areas that require more focus. The first such systematic studies that separately address the relative contributions of solvation, aggregational, and interfacial effects within a common ground are still very rare. Second, the relationship between environmental complexity and excited-state dynamics remains poorly understood. Third, we need scalable multiscale methodologies that combine quantum-mechanical accuracy with realistic environmental representation. Filling these gaps will be essential to accelerate the transition of environment-resolved computational spectroscopy from qualitative interpretation to quantitative prediction. In this sense, Fig. 3 illustrates methodological areas that require greater effort . 4.8. Synthesis and Implications In sum, the thematic synthesis presented herein identifies environmental effects as key controls on spectroscopic features and CT mechanisms in DFT/TDDFT/sci-X calculations. The cross-application-domain evidence presented here shows that ER models are not a niche area of research but an obligatory stage in the development of computational spectroscopy. Moreover, the distinction between core thematic studies and supporting studies in Supplementary Table S2 reinforces the validity of the trends discussed here. It provides clear grounding for the conclusions made in this section. 5. Conclusions This systematic literature review demonstrates that environmental effects are fundamental determinants of spectroscopic signatures and charge-transfer mechanisms in DFT/TDDFT-based studies, rather than secondary perturbations to isolated-molecule descriptions. Across diverse application domains—including molecular chromophores, fluorescent sensors, photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces—the reviewed literature consistently shows that solvation structure, molecular aggregation, and interfacial electric fields reshape excited-state electronic structure in ways that conventional single-molecule TDDFT approaches cannot capture. By synthesizing evidence from core thematic studies, this review establishes a coherent environment-resolved paradigm for computational spectroscopy, in which increasing environmental realism systematically enhances the interpretability and predictive reliability of spectroscopic simulations. Explicit microsolvation, aggregation modeling, and interface- or field-resolved approaches are particularly critical for systems governed by charge transfer, polarization, or collective electronic effects. Importantly, the analysis highlights that environmental modeling and electronic-structure methodology are intrinsically coupled: improvements in one without appropriate consideration of the other yield limited predictive gains. Beyond consolidating current knowledge, this review identifies persistent methodological gaps that constrain progress in the field. These include inconsistent validation against experimental spectra, limited ensemble sampling, insufficient treatment of collective and interfacial effects, and a lack of standardized reporting practices. Addressing these gaps is essential for advancing computational spectroscopy from qualitative interpretation toward quantitative prediction. Declarations Acknowledgements We would like to thank Endang Hariningsih for her guidance in using systematic literature review class, and Agnes Suyanto who provided constructive comments on this paper. Author contributions All authors contributed to the conception and design of the study. Frans Augusthinus Asmuruf, Jonathan Kiwasi Wororomi, Yohanis Irenius Mandik, Yuliana Ruth Yabansabra, and Eva Susanty Simaremare, performed material preparation, data collection, and analysis. Frans Augusthinus Asmuruf wrote the first draft of the manuscript, and all authors provided comments on previous versions. All authors read and approved the final manuscript. Funding This work was supported by the Graduate School of Cenderawasih University grant [1671/UN20.2.1/PG/2025] Data availability All relevant data generated or analyzed during the work are included in this paper and any additional data can be made available upon reasonable request. Conflict of interest The authors declare that they have no conflict of interest. Consent to Publish Not applicable. Ethics Approval and Consent to Participate Not applicable. References Jacoby Morris K, et al. 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Synthesis, crystal structure, DFT calculation and trans→cis isomerisation studies of bipyridyl ruthenium(II) complexes bearing 8-oxyquinolate azo ligands. J Chem Sci. 2020;132:1. https://doi.org/10.1007/s12039-020-01846-6 . Hassan AU, et al. Novel pull–push organic switches with D–π–A structural designs: computational design of star shape organic materials. Struct Chem. 2023;34:399–412. https://doi.org/10.1007/s11224-022-01983-3 . Nitika SK, Dixit, Abbas H. Excited state and charge transfer dynamics in gas phase molecule of CH3NH3PbI3: first-principles study. J Mol Model. 2021;27:27. https://doi.org/10.1007/s00894-020-04635-7 . Wu Y, Yan L, Qian Y, Gao Y. Theoretical study of the structures and properties of WLin (n = 2–12) bimetallic clusters. J Cluster Sci. 2023;34:3087–93. https://doi.org/10.1007/s10876-023-02449-0 . Hema, et al. Computational study of the intermolecular interactions and their effect on the UV–visible spectra of the ternary liquid mixture of benzene, ethanol, and propylene glycol. J Mol Model. 2020;26:10. https://doi.org/10.1007/s00894-020-04533-y . Joy S, Periyasamy G. Influence of explicit water molecules on the charge migration dynamics of peptidomimetics: a DFT study. Theor Chem Acc. 2020;139:5. https://doi.org/10.1007/s00214-020-02609-9 . Moreira JM, et al. Copper(II) complexes with novel Schiff-based ligands: synthesis, crystal structure, thermal, spectroscopic and theoretical studies. J Therm Anal Calorim. 2022;147:4087–98. https://doi.org/10.1007/s10973-021-10803-5 . Moitra T, Konecny L, Kadek M, Rubio A, Repisky M. Accurate relativistic real-time time-dependent density functional theory for valence and core attosecond transient absorption spectroscopy. J Phys Chem Lett. 2023. https://doi.org/10.1021/acs.jpclett.2c03599 . Mahmoudi S, Dehkordi MM, Asgarshamsi MH. Density functional theory studies of antioxidants: a review. J Mol Model. 2021. https://doi.org/10.1007/s00894-021-04891-1 . Baniasadi F, Fathi MB, Tehranchi MM, Amani V. Study of UV–Vis absorption spectra of magnetic molecule tripyridinium bis[tetrabromidoferrate(III)] bromide with density functional formalisms. Scientia Iranica. 2022;29:1319–29. https://doi.org/10.24200/sci.2021.57647.5342 . Yang B, Huang S. A structure and spectroscopy study about [16]cycloparaphenylene chiral molecule. Theor Chem Acc. 2023;142:7. https://doi.org/10.1007/s00214-023-02999-6 . Coppola F, Carfora R, Cimino P, Petrone A, Rega N. Tetracyanoethylene Na+/K+ radical anion coordination sites unveiled via electronic and vibrational fingerprints. Theor Chem Acc. 2024;143:12. https://doi.org/10.1007/s00214-024-03151-8 . Mohammadtabar F, Rajaie Khorasani R, Mohammadi-Manesh H, Kazempour A. Distinguishing damaged DNA bases: a detailed TDDFT study of the HHG and optical absorption cross-section spectra of DNA adducts. Theor Chem Acc. 2025;144:5. https://doi.org/10.1007/s00214-025-03190-9 . Sidorin AE, et al. Electronic structure, cationic, and excited states of nitrogen-containing spiroborates. J Mol Model. 2023;29:3. https://doi.org/10.1007/s00894-023-05465-z . Cruz ÁB, et al. Theoretical and experimental study of the diastereoisomers (2S) and (2R)-naringenin-6-C-β-D-glucopyranoside obtained from Clitoria guianensis. J Mol Model. 2023;29:3. https://doi.org/10.1007/s00894-023-05482-y . Montserrat R, Oliveira RR, Rocha AB. Total absorption spectrum of benzene aggregates obtained from two different approaches. J Mol Model. 2024;30:3. https://doi.org/10.1007/s00894-024-05859-7 . Latif A, Latif A, Mohsin M, Bhatti IA. Density functional theory for nanomaterials: structural and spectroscopic applications. J Mol Model. 2025. https://doi.org/10.1007/s00894-025-06431-7 . Heryanto H, Ardiansyah A, Rahmat R, Tahir D. Science mapping analysis of density functional theory for material design: a review. JOM. 2024;76:4629–42. https://doi.org/10.1007/s11837-024-06644-w . Popay J et al. (2006) Guidance on the conduct of narrative synthesis in systematic reviews. Greenhalgh T, Thorne S, Malterud K. Time to challenge the spurious hierarchy of systematic over narrative reviews? Eur J Clin Invest. 2018;48:6. https://doi.org/10.1111/eci.12931 . Additional Declarations No competing interests reported. Supplementary Files TableS1MasterSLRFilledv4.xlsx TableS2Supplementaryinformation.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8815313","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":600244484,"identity":"91e0829e-1381-4bc4-b018-2faf4ffe7eb1","order_by":0,"name":"Frans Augusthinus Asmuruf","email":"data:image/png;base64,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","orcid":"","institution":"The University of Cenderawasih","correspondingAuthor":true,"prefix":"","firstName":"Frans","middleName":"Augusthinus","lastName":"Asmuruf","suffix":""},{"id":600244487,"identity":"5f6ce139-fad4-4ae8-b41a-46af976df07f","order_by":1,"name":"Yohanis Irenius Mandik","email":"","orcid":"","institution":"The University of Cenderawasih","correspondingAuthor":false,"prefix":"","firstName":"Yohanis","middleName":"Irenius","lastName":"Mandik","suffix":""},{"id":600244488,"identity":"6e8d1456-749e-4c33-a9db-0e88611680ff","order_by":2,"name":"Yuliana Ruth Yabansabra","email":"","orcid":"","institution":"The University of Cenderawasih","correspondingAuthor":false,"prefix":"","firstName":"Yuliana","middleName":"Ruth","lastName":"Yabansabra","suffix":""},{"id":600244491,"identity":"a711bf72-ac00-4804-b06f-cc584754f749","order_by":3,"name":"Jonathan Kiwasi Wororomi","email":"","orcid":"","institution":"The University of Cenderawasih","correspondingAuthor":false,"prefix":"","firstName":"Jonathan","middleName":"Kiwasi","lastName":"Wororomi","suffix":""},{"id":600244493,"identity":"00acad5c-ecc9-47a0-ba24-632e65b5c15a","order_by":4,"name":"Eva Susanty Simaremare","email":"","orcid":"","institution":"The University of Cenderawasih","correspondingAuthor":false,"prefix":"","firstName":"Eva","middleName":"Susanty","lastName":"Simaremare","suffix":""}],"badges":[],"createdAt":"2026-02-07 12:09:17","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-8815313/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8815313/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":103933251,"identity":"63fe591e-d0a8-41c8-8629-a5f312ccd273","added_by":"auto","created_at":"2026-03-04 17:04:21","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":210048,"visible":true,"origin":"","legend":"\u003cp\u003eConceptual framework illustrating hierarchical modeling strategies in DFT/TDDFT-based computational spectroscopy. The framework progresses from isolated-molecule calculations to increasingly environment-resolved approaches, including implicit solvation, explicit microsolvation, aggregation or packing models, and interface and field-resolved representations. As environmental realism increases, spectroscopic predictions more accurately capture charge-transfer character, polarization effects, and experimentally observed spectral signatures.\u003c/p\u003e","description":"","filename":"floatimage1.png","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/34dc465844e82639a4ecd951.png"},{"id":103933248,"identity":"856ca6a8-56cf-4f6e-92b7-d36894d94666","added_by":"auto","created_at":"2026-03-04 17:04:20","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":511936,"visible":true,"origin":"","legend":"\u003cp\u003ePRISMA flow diagram illustrating the systematic review design and study selection process applied in this work. Literature records were identified through structured searches in major scientific databases, followed by duplicate removal, abstract screening, and full-text eligibility assessment. The final set of included studies constitutes the corpus used for qualitative thematic synthesis and critical discussion of environment-resolved DFT/TDDFT-based spectroscopic modeling. The review protocol and reporting structure adhere to the PRISMA 2020 guidelines.\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/8d5894bf62f97ee265a14036.jpeg"},{"id":103933253,"identity":"3325a7e2-6a75-4e5d-b3d0-0da9748e56ff","added_by":"auto","created_at":"2026-03-04 17:04:21","extension":"jpeg","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":669765,"visible":true,"origin":"","legend":"\u003cp\u003eApplication-domain map of DFT/TDDFT-based computational spectroscopy. The diagram summarizes the major application domains identified in the reviewed literature, including (i) excited-state processes in molecular chromophores, (ii) fluorescent sensors and analytical spectroscopy, (iii) photoactive materials for energy conversion, (iv) supramolecular assemblies and metal–organic frameworks, (v) nanoclusters and finite-size systems, and (vi) advanced spectroscopic modalities and hybrid interfaces. Overlapping regions indicate shared methodological challenges, particularly the need for environment-resolved modeling to describe charge-transfer mechanisms and spectroscopic signatures across domains accurately.\u003c/p\u003e","description":"","filename":"floatimage3.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/3fd34b1e8fab6dca2314ac72.jpeg"},{"id":103933250,"identity":"c189486a-cf83-4f9c-8e58-d72b1ddbe321","added_by":"auto","created_at":"2026-03-04 17:04:20","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":174082,"visible":true,"origin":"","legend":"\u003cp\u003eSchematic representation of the relationship between environmental complexity, computational cost, and spectroscopic reliability in DFT/TDDFT-based studies. Implicit solvation models offer low computational cost but limited accuracy for charge-transfer-dominated systems, whereas microsolvation, aggregation, and interface-resolved approaches provide enhanced spectroscopic fidelity at increased computational expense. Regions highlighted as having methodological gaps indicate where improved modeling strategies and standardization are most needed.\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/14c0c44eb899b2cba4f7dd35.png"},{"id":108991911,"identity":"8781cd26-5705-4bbe-a73f-fc949c4fabc2","added_by":"auto","created_at":"2026-05-11 13:30:58","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1927329,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/4c815a9a-40ec-44d3-8524-23ab5188f6e0.pdf"},{"id":103933249,"identity":"6d112514-31c3-4171-853b-3970472ed031","added_by":"auto","created_at":"2026-03-04 17:04:20","extension":"xlsx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":21546,"visible":true,"origin":"","legend":"","description":"","filename":"TableS1MasterSLRFilledv4.xlsx","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/304884910f8f2172df36dfbe.xlsx"},{"id":104401925,"identity":"021e1aa7-ed68-4fbb-b1ad-98be397455ff","added_by":"auto","created_at":"2026-03-11 12:13:55","extension":"docx","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":13373,"visible":true,"origin":"","legend":"","description":"","filename":"TableS2Supplementaryinformation.docx","url":"https://assets-eu.researchsquare.com/files/rs-8815313/v1/d1e1a5b6fc831484e87add45.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Beyond Isolated-Molecule TDDFT: Solvation, Aggregation, and Interfacial Fields in Predicting Spectroscopic Signatures and Charge-Transfer Mechanisms – A Systematic Review","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eDensity functional theory (DFT) and time-dependent density functional theory (TDDFT) are nowadays essential methods in contemporary computational chemistry to understand and predict spectroscopic properties\u0026ensp;of molecular and materials systems [\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. In the last decades, TDDFT\u0026ensp; has been increasingly used to simulate electronic absorption and emission spectra, excited-state processes, and charge transfer in diverse chemical settings [\u003cspan additionalcitationids=\"CR3 CR4\" citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e], ranging from molecular chromophores to fluorescent sensors, active photo-materials, and hybrid interfaces. Because TDDFT offers a good compromise between efficient calculations and satisfactory accuracy, it is increasingly used as a\u0026ensp;complement to experimental spectroscopy.\u003c/p\u003e \u003cp\u003eDespite their striking success, TDDFT-based spectral simulations still rely on isolated-molecule descriptions, with only rough simplifications of\u0026ensp; their immediate environment (e.g., an implicit dielectric model) [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. In\u0026ensp; such schemes, molecules are treated as independent, all-electron particles, and the environment is included only through homogeneous screening. Although such methods may be adequate\u0026ensp; for the qualitative interpretation of results in weakly interacting systems, they are now recognized as inadequate for excited states that display large charge-transfer character [\u003cspan additionalcitationids=\"CR9\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], strong polarization, or sensitivity to local structural ordering.\u003c/p\u003e \u003cp\u003eIt is acknowledged that, in realistic chemical environments, the\u0026ensp; spectroscopic fingerprints are seldom due solely to intrinsic molecular features. On the contrary, solvation structure, molecular aggregation, and interfacial electric field are often crucial in determining excited-state potential energy surfaces, transition\u0026ensp; density, and oscillator strength [\u003cspan additionalcitationids=\"CR12 CR13\" citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. There is a large body of computational and experimental work supporting the\u0026ensp; idea that explicit solute\u0026ndash;solvent effects can significantly shift excitation and emission energies, modify excited-state orderings, and reassign mechanisms in photoinduced processes such as intramolecular charge transfer or periodic reactions [\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Aggregation or packing effects in condensed phases can similarly introduce collective excited states that are absent\u0026ensp; from single-molecule descriptions and dominate observed spectroscopic responses [\u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThese\u0026ensp; restrictions are especially pronounced in systems in which spectroscopy directly correlates with function. In the case of fluorescent and sensing probes, the solvating and coordinating environment has been shown to\u0026ensp;directly control sensitivity and selectivity [\u003cspan additionalcitationids=\"CR24\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e]. Aggregation-induced electronic\u0026ensp; coupling and interfacial polarization in photoactive materials for optoelectronics and energy conversion govern the onset of absorption and emission pathways and charge-separation efficiency [\u003cspan additionalcitationids=\"CR27\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. At hybrid interfaces between dyes and semiconductors, or in perovskite-based heterostructures, local electric fields\u0026ensp; and electronic alignment can radically alter charge-transfer properties and spectroscopic signatures [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e]. In this situation, spectroscopic predictions made using TDDFT models of isolated molecules are likely to give an incomplete or incorrect physical\u0026ensp;picture.\u003c/p\u003e \u003cp\u003eThese findings reveal fundamental conceptual and computational insufficiencies\u0026ensp;of the isolated-molecule TDDFT formalism. In many of the current systems of interest, such as thermally activated delayed fluorescence (TADFs) emitters, metal-organic frameworks, nanoclusters, and interfacial assemblies [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e], spectral features arise from environment-mediated electronic\u0026ensp; interactions rather than from isolated chromophores. Hence, the view that environmental degrees of freedom are not simply perturbations but must be considered as part of, and integrated into, the electronic-structure problem is\u0026ensp; becoming increasingly widespread.\u003c/p\u003e \u003cp\u003eIn addressing these\u0026ensp; challenges, a methodological transition has been made in recent years toward environmentally resolved computational spectroscopy: a hierarchy of modeling methods, from coarse-grained to all-atom, for the molecules of interest [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e]. These strategies cover implicit solvation models, explicit microsolvation, aggregation and packing\u0026ensp; models, and interface- or field-resolved approaches. Although these approaches have proven beneficial across a range of studies, their application has been partial; no consistent recommendation exists on the desirable minimum level of habitat heterogeneity and its\u0026ensp; nature (i.e., whether it should be added in an artificial form or as reintroduced natural elements) [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eFigure 1. Conceptual framework illustrating hierarchical modeling strategies in DFT/TDDFT-based computational spectroscopy. The framework progresses from isolated-molecule calculations to increasingly environment-resolved approaches, including implicit solvation, explicit microsolvation, aggregation or packing models, and interface and field-resolved representations. As environmental realism increases, spectroscopic predictions more accurately capture charge-transfer character, polarization effects, and experimentally observed spectral signatures.\u003c/p\u003e \u003cp\u003eThe conceptual framework of\u0026ensp; this review is depicted in Fig.\u0026nbsp;1, emphasizing the continuum from isolated-molecule TDDFT to increasingly environment-defined spectral modeling. Schematically, the incorporation of solvation, aggregation, and interfacial effects also \u0026ensp;gives rise to additional electronic interactions that significantly alter excited-state properties and spectroscopic fingerprints, calling for environment-adaptive computational tools (48).\u003c/p\u003e \u003cp\u003eIn this light, a comprehensive compilation of the field of environment-aware DFT/TDDFT spectroscopy is\u0026ensp; due and timely. The existing reviews typically focus solely on\u0026ensp; methodological advances in TDDFT or on specific application fields, without placing solvation, aggregation, and interfacial effects as a unified theoretical concept clearly at the core [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. As a result, the broader relevance of environmental\u0026ensp; effects for spectroscopic modeling and their interplay with intrinsic limitations of TDDFT are not well articulated.\u003c/p\u003e \u003cp\u003eIn this \u0026ensp;contribution, we review the literature on spectroscopic studies using DFT and TD-DFT, with particular emphasis on environmental effects. In this review, we adopt a PRISMA-like review\u0026ensp; design [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e] to assess a wide range of recent literature on molecular chromophores, sensors, and photoactive materials, as well as supramolecular assemblies, nanoclusters, and hybrid interfaces. This review has three main goals: (i) to survey application domains and modeling approaches that dominate in environment-aware computational spectroscopy, (ii) to critically evaluate how solvation, aggregation\u0026ensp;, or interfacial fields can affect both spectroscopic signatures and charge-transfer mechanisms, and (iii) to point out methodological/interpretative shortcomings as well as advice for best-practice decisions. The purpose of such an accumulation is to provide context and perspective, consolidating knowledge across diverse systems to broaden what\u0026ensp; remain largely case-specific methodologies into a more coherent and predictive modeling paradigm for environment-resolved TDDFT spectroscopy.\u003c/p\u003e"},{"header":"2. Methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003e2.1. Review Design and Reporting Framework\u003c/h2\u003e \u003cp\u003eThis study was conducted as a systematic literature review (SLR) following the principles and reporting standards of the PRISMA 2020 guidelines [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. The PRISMA framework was adopted to ensure transparency, reproducibility, and methodological rigor in the identification, screening, eligibility assessment, and inclusion of relevant studies. A PRISMA-based workflow was implemented to define the scope of the review, minimize selection bias, and provide a clear audit trail of the study selection process.\u003c/p\u003e \u003cp\u003eThe overall review design and study selection process are summarized in the PRISMA flow diagram shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e. The diagram provides a transparent overview of the identification, screening, eligibility assessment, and final inclusion of studies analyzed in this review, ensuring methodological rigor and reproducibility in accordance with the PRISMA 2020 guidelines.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003e2.2. Literature Search Strategy\u003c/h2\u003e \u003cp\u003eA structured and comprehensive literature search was performed across major scientific databases, including Web of Science and Scopus, which collectively provide broad coverage of journals in computational chemistry, spectroscopy, and materials science. Additional records were identified through publisher platforms associated with Springer Nature, Elsevier, ACS Publications, and the Nature Portfolio.\u003c/p\u003e \u003cp\u003eSearch queries were constructed using combinations of methodological and application-oriented keywords to capture studies employing DFT or TDDFT for spectroscopic analysis. Representative search strings included:\u003cdiv class=\"BlockQuote\"\u003e\u003cp\u003eDFT\u0026rdquo; OR \u0026ldquo;TDDFT\u0026rdquo; AND \u0026ldquo;spectroscopy\u003c/p\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003e\"time-dependent density functional theory\" AND \"UV\u0026ndash;Vis\" OR \"fluorescence\"\u003c/p\u003e \u003cp\u003e\"TDDFT\" AND \"charge transfer\" AND (\"solvation\" OR \"aggregation\" OR \"interface\").\u003c/p\u003e \u003cp\u003eThe search strategy was iteratively refined to balance sensitivity and specificity, following best practices for systematic reviews in computational and interdisciplinary research [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec5\" class=\"Section2\"\u003e \u003ch2\u003e2.3. Inclusion and Exclusion Criteria\u003c/h2\u003e \u003cp\u003eThe inclusion criteria were developed in advance to promote uniformity and the usefulness of\u0026ensp; applied content.\u003c/p\u003e \u003cp\u003eInclusion criteria were:\u003c/p\u003e \u003cp\u003e \u003cul\u003e \u003cli\u003e \u003cp\u003eOriginal peer-reviewed research articles.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eUse of the DFT\u0026ensp; and/or TDDFT.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eEmphasis on spectroscopic properties (i.e., electronic absorption, emission, vibrational, electroabsorption,\u0026ensp; or X-ray spectroscopies).\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eExcited states, charge-transfer processes, or spectroscopic\u0026ensp;signatures of interest for either molecular or materials systems.\u003c/p\u003e \u003c/li\u003e \u003c/ul\u003e \u003c/p\u003e \u003cp\u003eExclusion criteria were:\u003c/p\u003e \u003cp\u003e \u003cul\u003e \u003cli\u003e \u003cp\u003eReview articles, perspectives, or editorials.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eStudies lacking a spectroscopic component.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eMethodological\u0026ensp; developments only; not applied to spectral interpretation.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eArticles with inadequate methodological information for\u0026ensp; the assessment of computational reliability.\u003c/p\u003e \u003c/li\u003e \u003c/ul\u003e \u003c/p\u003e \u003cp\u003eThese inclusion\u0026ensp; and exclusion criteria are maintained throughout record screening and eligibility assessment.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003e2.4. Screening and Study Selection\u003c/h2\u003e \u003cp\u003eAll relevant information from database\u0026ensp; searches was imported in the first round, and duplicates were filtered out. The titles and\u0026ensp;abstracts were reviewed in order to discard those studies that could be easily assumed not to fall within the field of DFT/TDDFT-based spectroscopy. Full-text screening was then conducted to assess\u0026ensp; eligibility according to the predetermined inclusion and exclusion criteria.\u003c/p\u003e \u003cp\u003eThe last set of retained studies comprises \u0026ensp;the sample we analyzed in Section \u003cspan refid=\"Sec10\" class=\"InternalRef\"\u003e3\u003c/span\u003e and will serve as the source of evidence for our descriptive mapping (Section \u003cspan refid=\"Sec10\" class=\"InternalRef\"\u003e3\u003c/span\u003e) and thematic synthesis (Section \u003cspan refid=\"Sec16\" class=\"InternalRef\"\u003e4\u003c/span\u003e). The selection\u0026ensp;of studies is clearly noted in the PRISMA flow diagram presented in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003e2.5. Data Extraction and Classification\u003c/h2\u003e \u003cp\u003eFor each included study, structured data extraction was carried out using a predefined extraction matrix corresponding to Supplementary Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e (Master SLR Table). Extracted information included bibliographic details, application domain, spectroscopic modality, computational methodology (DFT, TDDFT, or variants), and the treatment of environmental effects.\u003c/p\u003e \u003cp\u003eTo enable cross-study comparison, each article was classified according to:\u003c/p\u003e \u003cp\u003e \u003cul\u003e \u003cli\u003e \u003cp\u003eApplication domain, following the taxonomy summarized in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e (e.g., molecular chromophores, sensors, photoactive materials, supramolecular assemblies, nanoclusters, and interfaces).\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eEnvironmental treatment, including gas-phase or isolated-molecule models, implicit solvation, explicit microsolvation, aggregation or packing models, and interface- or field-resolved approaches.\u003c/p\u003e \u003c/li\u003e \u003cli\u003e \u003cp\u003eAnalytical role, distinguishing between \u003cem\u003ecore thematic studies\u003c/em\u003e and \u003cem\u003esupporting studies\u003c/em\u003e, as summarized in Supplementary Table \u003cspan refid=\"MOESM2\" class=\"InternalRef\"\u003eS2\u003c/span\u003e.\u003c/p\u003e \u003c/li\u003e \u003c/ul\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003e2.6. Quality Appraisal\u003c/h2\u003e \u003cp\u003eMethodological quality was assessed qualitatively rather than through numerical scoring, in line with recommendations for systematic reviews involving heterogeneous computational methodologies [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. The appraisal focused on the transparency of computational details, the adequacy of environmental modeling, validation against experimental data or higher-level theoretical methods, and the consistency of spectroscopic assignments.\u003c/p\u003e \u003cp\u003eStudies were not excluded solely based on methodological limitations; instead, quality considerations informed the weighting of evidence during thematic synthesis.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003e2.7. Synthesis Strategy\u003c/h2\u003e \u003cp\u003eGiven the diversity of systems, spectroscopic techniques, and computational strategies represented in the reviewed literature, a narrative thematic synthesis approach was adopted [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. This approach emphasizes identifying recurring mechanistic patterns, methodological trends, and research gaps rather than quantitative aggregation.\u003c/p\u003e \u003cp\u003eThe synthesis integrates evidence across application domains to elucidate how solvation, aggregation, and interfacial effects systematically influence spectroscopic signatures and charge-transfer mechanisms in DFT/TDDFT-based studies.\u003c/p\u003e \u003c/div\u003e"},{"header":"3. Results","content":"\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003e3.1. Overview of the Reviewed Corpus\u003c/h2\u003e \u003cp\u003eFollowing the eligibility assessment, 92 peer-reviewed articles met the inclusion criteria (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e2\u003c/span\u003e). Of these, 83 studies formed the final analytical corpus for thematic synthesis, while the remaining studies were retained as contextual or supporting references and not included in the core thematic analysis. These studies span a broad temporal range, with a clear concentration in the last five to seven years, reflecting growing interest in environment-aware spectroscopic modeling using DFT and TDDFT. The reviewed literature encompasses a diverse set of molecular and materials systems, spectroscopic techniques, and computational strategies, underscoring the methodological and application-driven heterogeneity of the field.\u003c/p\u003e \u003cp\u003eAcross the corpus, TDDFT emerges as the dominant computational approach for modeling electronic absorption and emission spectra, frequently complemented by ground-state DFT calculations for structural optimization and electronic analysis. Variants such as the Tamm\u0026ndash;Dancoff approximation (TDA), long-range corrected functionals, and hybrid exchange\u0026ndash;correlation schemes are commonly employed to mitigate known deficiencies of conventional TDDFT, particularly in systems with significant charge-transfer character [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e]. The search strategy was iteratively refined to balance sensitivity and specificity, following best practices for systematic reviews in computational and interdisciplinary research [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eTo provide an integrated overview of the reviewed literature, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e maps the major application domains addressed by DFT/TDDFT-based spectroscopic studies. The figure highlights the diversity of systems investigated, ranging from molecular chromophores and fluorescent sensors to photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces, while also illustrating shared methodological challenges across domains.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003e3.2. Dominant Application Domains\u003c/h2\u003e \u003cp\u003eAnalysis of the reviewed studies reveals six major application domains, as summarized schematically in Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e.\u003c/p\u003e \u003cp\u003e \u003cem\u003eMolecular Chromophores and Excited-State Processes\u003c/em\u003e \u003c/p\u003e \u003cp\u003eA substantial portion of the literature focuses on molecular chromophores exhibiting intramolecular charge transfer, excited-state proton transfer, or solvatochromic behavior. In these studies, TDDFT is used to assign electronic transitions, rationalize spectral shifts, and elucidate excited-state relaxation pathways [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e, \u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Environmental effects are frequently invoked to explain discrepancies between gas-phase calculations and experimental spectra, particularly in polar solvents.\u003c/p\u003e \u003cp\u003e \u003cem\u003eFluorescent Sensors and Analytical Spectroscopy\u003c/em\u003e \u003c/p\u003e \u003cp\u003eAnother prominent application domain involves fluorescent and chemosensory systems designed for chemical or biological detection. Here, spectroscopic responses are often highly sensitive to solvation, coordination, and local electrostatic environments. TDDFT-based studies in this domain commonly incorporate implicit or explicit solvation models to rationalize emission shifts, fluorescence quenching, or enhancement mechanisms [\u003cspan additionalcitationids=\"CR24\" citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003ePhotoactive Materials for Energy Conversion\u003c/em\u003e \u003c/p\u003e \u003cp\u003ePhotoactive materials, including organic photovoltaics, dye-sensitized systems, and light-emitting materials, constitute a third major domain. In these systems, aggregation-induced electronic coupling and interfacial effects play central roles in determining absorption onsets and charge-separation efficiencies. The reviewed studies highlight the need to model intermolecular interactions and interfaces to capture experimentally observed spectroscopic trends [\u003cspan additionalcitationids=\"CR27 CR28\" citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eSupramolecular Assemblies and Metal\u0026ndash;Organic Frameworks\u003c/em\u003e \u003c/p\u003e \u003cp\u003eSeveral studies address supramolecular assemblies and metal\u0026ndash;organic frameworks, where collective electronic effects and host\u0026ndash;guest interactions dominate spectroscopic behavior. TDDFT calculations in these systems frequently move beyond isolated-molecule models to include cluster or periodic representations, enabling more accurate interpretation of experimental spectra [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eNanoclusters and Finite-Size Systems\u003c/em\u003e \u003c/p\u003e \u003cp\u003eNanoclusters and finite-size systems represent another growing application area. In these studies, size-dependent electronic structure, surface effects, and environmental interactions are critical for understanding spectroscopic signatures. The reviewed literature demonstrates that environmental modeling is essential for capturing the interplay between quantum confinement and external perturbations [\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e, \u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eAdvanced Spectroscopic Modalities and Hybrid Interfaces\u003c/em\u003e \u003c/p\u003e \u003cp\u003eA smaller but increasingly significant subset of studies explores advanced spectroscopic techniques, such as electroabsorption and X-ray spectroscopies, as well as hybrid interfaces involving metals, semiconductors, or electrodes. These systems often require explicit treatment of interfacial fields and electronic coupling to reproduce experimental observables [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec13\" class=\"Section2\"\u003e \u003ch2\u003e3.3. Treatment of Environmental Effects\u003c/h2\u003e \u003cp\u003eAcross all application domains, the reviewed studies employ a range of strategies to incorporate environmental effects into DFT/TDDFT calculations.\u003c/p\u003e \u003cp\u003e \u003cem\u003eIsolated-Molecule and Implicit Solvation Models\u003c/em\u003e \u003c/p\u003e \u003cp\u003eIsolated-molecule models, with or without implicit solvation, remain widely used due to their computational efficiency. Implicit solvation models, such as polarizable continuum approaches, are often sufficient to reproduce general solvatochromic trends but frequently fail to capture specific solute\u0026ndash;environment interactions or state-specific polarization effects [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eExplicit Microsolvation and Cluster Models\u003c/em\u003e \u003c/p\u003e \u003cp\u003eExplicit microsolvation approaches, in which solvent molecules or coordinating species are explicitly included within the quantum-mechanical region, are increasingly adopted to capture hydrogen bonding, directional interactions, and local structural effects. Studies employing these models report improved agreement with experimental spectra and more reliable mechanistic interpretations, particularly for charge-transfer and proton-transfer processes [\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eAggregation and Packing Effects\u003c/em\u003e \u003c/p\u003e \u003cp\u003eAggregation effects are commonly modeled using dimeric, oligomeric, or cluster representations. These approaches reveal the emergence of collective excited states and excitonic coupling that are absent in isolated-molecule calculations. The reviewed literature indicates that aggregation-induced spectral shifts and intensity changes are often dominant in condensed-phase systems [\u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cem\u003eInterface- and Field-Resolved Approaches\u003c/em\u003e \u003c/p\u003e \u003cp\u003eFor hybrid interfaces and electroactive systems, explicit modeling of interfaces or external fields is required to capture charge-transfer energetics and spectroscopic responses. Although computationally demanding, such approaches provide critical insights into systems in which interfacial polarization and electronic alignment dictate function [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec14\" class=\"Section2\"\u003e \u003ch2\u003e3.4. Methodological Trends and Validation Practices\u003c/h2\u003e \u003cp\u003eMethodological analysis of the reviewed corpus reveals an increasing use of long-range-corrected functionals and benchmarking against experimental spectra. However, validation practices remain inconsistent across studies. While some works report quantitative agreement with experimental excitation energies or spectral shapes, others rely primarily on qualitative comparisons. This variability highlights the need for standardized validation protocols in environment-resolved spectroscopic modeling [\u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec15\" class=\"Section2\"\u003e \u003ch2\u003e3.5. Classification of Core and Supporting Studies\u003c/h2\u003e \u003cp\u003eTo facilitate focused thematic synthesis, the reviewed studies were classified according to their analytical role. Core thematic studies explicitly compare isolated-molecule and environment-resolved models and demonstrate qualitative changes in spectroscopic signatures or charge-transfer mechanisms. Supporting studies, while methodologically relevant, primarily report incremental improvements or apply established approaches without systematic comparison.\u003c/p\u003e \u003cp\u003eThis classification, summarized in Supplementary Table \u003cspan refid=\"MOESM2\" class=\"InternalRef\"\u003eS2\u003c/span\u003e, underpins the thematic discussion presented in Section \u003cspan refid=\"Sec16\" class=\"InternalRef\"\u003e4\u003c/span\u003e and ensures transparency in the selection of evidence used for in-depth analysis.\u003c/p\u003e \u003c/div\u003e"},{"header":"4. Discussion","content":"\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e \u003ch2\u003e4.1. Reinterpreting Computational Spectroscopy\u0026ensp;Outside Isolated Molecules\u003c/h2\u003e \u003cp\u003eAlthough isolated-molecule TDDFT has historically been a useful starting point for spectroscopic modeling, the evidence presented in this review indicates that it no longer provides an adequate approximation for modern target systems. In several application areas, spectroscopic features and\u0026ensp; charge-transfer mechanisms are observed to arise from environment-mediated electronic interactions rather than from intrinsic molecular properties alone [\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. The analysed thematic core studies all confirm that ignoring environmental freedoms of motion can lead to quantitative errors and incorrect\u0026ensp; causal interpretations.\u003c/p\u003e \u003cp\u003eThis observation motivates a paradigm shift in how we think about computational spectroscopy, in which solvation, aggregation, and\u0026ensp; interfacial effects are considered part of the electronic-structure problem. Within this context-specific picture, TDDFT calculations are no longer viewed as stand-alone measurements of a molecular property, but rather as OCAs whose predictive ability is evaluated by their success or failure in simple, operational representations of environmental complexity [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e].\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec18\" class=\"Section2\"\u003e \u003ch2\u003e4.2. Solvation at the Active Site: An Essential\u0026ensp;Factor for Excited State Geometry\u003c/h2\u003e \u003cp\u003eSolvation\u0026ensp; effects are the most studied type of environmental impact in TDDFT spectroscopy. The literature reviewed here has demonstrated that solvation plays a role that goes far beyond simply\u0026ensp; uniformly stabilizing excited states; it actually modifies transition densities and state ordering while fostering charge localization, particularly in systems with strong ICT or PT character [\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eImplicit\u0026ensp; solvation schemes model nonspecific dielectric stabilization and often qualitatively predict the correct solvatochromic trend [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. However, the core theme studies clearly indicate that these\u0026ensp;models often do not accurately portray state-dependent polarisation and directionality of solute\u0026ndash;solvent interactions. Pure solvent or macroscopic polar\u0026ensp; environment models typically require empirical optimization of reorganization modes. However, explicit microsolvation methodologies directly account for hydrogen bonding and local coordination, yielding better agreement with experimental measurements and greater chemical validity [\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. These results indicate that solvation is more than an energy correction: \u0026ensp;in fact, it must be considered a structural and electronic modifier.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec19\" class=\"Section2\"\u003e \u003ch2\u003e4.3. Gatherings and Collective Excitations in\u0026ensp;Condensed Matter\u003c/h2\u003e \u003cp\u003eThe second principal axis along which the isolated-molecule TDDFT error can be decomposed is aggregation and packing effects. In the complex condensed-phase environment, excitonic coupling, electronic-state delocalization, and symmetry breaking lead to collective excited\u0026ensp; states that do not appear in single-molecule descriptions [\u003cspan additionalcitationids=\"CR20 CR21\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. The analyzed works show that aggregation-induced spectral\u0026ensp; shifts, intensity redistribution, and band broadening are often observed in the spectroscopic response.\u003c/p\u003e \u003cp\u003eNote that\u0026ensp;aggregation effects are not particular to crystalline or highly ordered systems. Even modestly bound\u0026ensp; dimers and other short-lived clusters can lead to qualitative alterations in the nature and selection rules of excited states. Dimeric or higher-oligomeric models are thus often the simplest required\u0026ensp; step beyond isolated molecules for qualitative spectroscopic analysis [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. These results highlight that aggregation is a general property of condensed-phase spectroscopy and\u0026ensp; not a system-specific artefact.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;4 schematically illustrates the trade-offs between environmental complexity, computational cost, and spectroscopic fidelity that emerge when moving beyond isolated-molecule TDDFT models. The theoretical areas where simplified models offer little physical\u0026ensp; insight, as well as those in which greater environmental fidelity leads to significant mechanistic advances but at higher computational cost, are addressed in the figure. These areas identify important methodological gaps and guide\u0026ensp; best-practice considerations in future environment-resolved TDDFT research.\u003c/p\u003e \u003cp\u003eFigure 4. Schematic representation of the relationship between environmental complexity, computational cost, and spectroscopic reliability in DFT/TDDFT-based studies. Implicit solvation models offer low computational cost but limited accuracy for charge-transfer-dominated systems, whereas microsolvation, aggregation, and interface-resolved approaches provide enhanced spectroscopic fidelity at increased computational expense. Regions highlighted as having methodological gaps indicate where improved modeling strategies and standardization are most needed.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec20\" class=\"Section2\"\u003e \u003ch2\u003e4.4. Interfacial fields and interfacial charge-transfer\u0026ensp;at hybrid interfaces\u003c/h2\u003e \u003cp\u003eHybrid interfaces introduce yet another layer of complexity due to local electric fields, electronic coupling, and\u0026ensp; energy-level alignment. The literature on dye\u0026ndash;semiconductor assemblies, metal\u0026ndash;molecule interfaces, and electroactive systems has\u0026ensp;documented that interfacial effects can drastically alter charge-transfer routes and spectroscopic signatures [\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e, \u003cspan additionalcitationids=\"CR31\" citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eExplicit results show that field-induced polarization and interfacial coupling profoundly influence excitation energies,\u0026ensp; oscillator strengths, and charge-separation efficiencies, beyond the range of gas-phase or bulk-solvation models. Although computationally intensive, explicit interface- or field-resolved models offer fundamental insight into systems that rely on interfacial behavior to\u0026ensp; function. These results emphasize that\u0026ensp; interfaces are unique spectroscopic environments that necessitate model strategies specifically designed for them, rather than extensions of solution-phase methods.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec21\" class=\"Section2\"\u003e \u003ch2\u003e4.5. Methodological Limitations of\u0026ensp;TDDFT within Environment-Resolved Frameworks\u003c/h2\u003e \u003cp\u003eThe inclusion of the environment in TDDFT\u0026ensp;responses reveals additional intrinsic limitations of the theory. Even with explicit inclusion of environmental complexity [\u003cspan additionalcitationids=\"CR9\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e], charge-transfer states, long-range polarization\u0026ensp;, and collective excitations push beyond what is treatable by usual exchange\u0026ndash;correlation functionals. The present review demonstrates that both long-range\u0026ensp; corrected functionals and TDA-based approaches can alleviate (though not fully correct) these problems.\u003c/p\u003e \u003cp\u003eAlso, the advantages of environment-resolved modeling\u0026ensp; depend strongly on the electronic-structure method used. Adding realism to the environment without restoring function becomes less and less rewarding; increasing methodological muscle in a monochromatic environment is still inadequate. It underscores the need for co-designing electronic-structure methods and environmental models for\u0026ensp; future spectroscopy studies.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec22\" class=\"Section2\"\u003e \u003ch2\u003e4.6. Validation Methods and\u0026ensp;the Requirement for Standardization\u003c/h2\u003e \u003cp\u003eThe absence of standardized validation benchmarks is a common theme\u0026ensp;throughout the literature reviewed. A few refactorings in our set have been reported to sh\u0026ensp;ow quantitative agreement with experimental spectra or to serve as benchmark cases against higher-level ab initio methods, rather than merely qualitative correspondence [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e]. Such heterogeneity hinders\u0026ensp; between-studies comparisons and reduces the field\u0026rsquo;s joint predictive strength (Hauner and Meier, 2003).\u003c/p\u003e \u003cp\u003eRecommendation: Good practice from the core thematic studies was to explicitly report on the environmental model construct, use ensemble sampling where\u0026ensp; applicable, and provide quantitative error metrics for spectral comparison. Such a practice would greatly\u0026ensp;improve the reproducibility and interpretation of environment-resolved TDDFT spectroscopies.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec23\" class=\"Section2\"\u003e \u003ch2\u003e4.7. Research Gaps and Future Directions\u003c/h2\u003e \u003cp\u003eHowever,\u0026ensp; there are still some research areas that require more focus. The first such systematic studies that separately address the relative contributions of solvation, aggregational, and\u0026ensp; interfacial effects within a common ground are still very rare. Second, the relationship between environmental complexity and excited-state dynamics remains poorly understood. Third, we\u0026ensp; need scalable multiscale methodologies that combine quantum-mechanical accuracy with realistic environmental representation.\u003c/p\u003e \u003cp\u003eFilling these gaps will be essential to accelerate the transition of environment-resolved computational spectroscopy from qualitative interpretation to quantitative\u0026ensp; prediction. In this sense, Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e3\u003c/span\u003e illustrates methodological areas that require greater effort\u0026ensp;.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec24\" class=\"Section2\"\u003e \u003ch2\u003e4.8. Synthesis and Implications\u003c/h2\u003e \u003cp\u003eIn sum, the thematic synthesis presented herein identifies environmental effects as key controls on spectroscopic features and CT mechanisms in DFT/TDDFT/sci-X\u0026ensp; calculations. The cross-application-domain evidence presented\u0026ensp; here shows that ER models are not a niche area of research but an obligatory stage in the development of computational spectroscopy.\u003c/p\u003e \u003cp\u003eMoreover, the distinction between core thematic studies and supporting studies in Supplementary\u0026ensp; Table \u003cspan refid=\"MOESM2\" class=\"InternalRef\"\u003eS2\u003c/span\u003e reinforces the validity of the trends discussed here. It provides clear grounding for the conclusions made in this section.\u003c/p\u003e \u003c/div\u003e"},{"header":"5. Conclusions","content":"\u003cp\u003eThis systematic literature review demonstrates that environmental effects are fundamental determinants of spectroscopic signatures and charge-transfer mechanisms in DFT/TDDFT-based studies, rather than secondary perturbations to isolated-molecule descriptions. Across diverse application domains\u0026mdash;including molecular chromophores, fluorescent sensors, photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces\u0026mdash;the reviewed literature consistently shows that solvation structure, molecular aggregation, and interfacial electric fields reshape excited-state electronic structure in ways that conventional single-molecule TDDFT approaches cannot capture.\u003c/p\u003e \u003cp\u003eBy synthesizing evidence from core thematic studies, this review establishes a coherent environment-resolved paradigm for computational spectroscopy, in which increasing environmental realism systematically enhances the interpretability and predictive reliability of spectroscopic simulations. Explicit microsolvation, aggregation modeling, and interface- or field-resolved approaches are particularly critical for systems governed by charge transfer, polarization, or collective electronic effects. Importantly, the analysis highlights that environmental modeling and electronic-structure methodology are intrinsically coupled: improvements in one without appropriate consideration of the other yield limited predictive gains.\u003c/p\u003e \u003cp\u003eBeyond consolidating current knowledge, this review identifies persistent methodological gaps that constrain progress in the field. These include inconsistent validation against experimental spectra, limited ensemble sampling, insufficient treatment of collective and interfacial effects, and a lack of standardized reporting practices. Addressing these gaps is essential for advancing computational spectroscopy from qualitative interpretation toward quantitative prediction.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAcknowledgements\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eWe would like to thank Endang Hariningsih for her guidance in using systematic literature review class, and Agnes Suyanto who provided constructive comments on this paper.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAuthor contributions\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll authors contributed to the conception and design of the study. Frans Augusthinus Asmuruf, Jonathan Kiwasi Wororomi, Yohanis Irenius Mandik, Yuliana Ruth Yabansabra, and Eva Susanty Simaremare, performed material preparation, data collection, and analysis. Frans Augusthinus Asmuruf wrote the first draft of the manuscript, and all authors provided comments on previous versions. All authors read and approved the final manuscript.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eFunding\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThis work was supported by the Graduate School of Cenderawasih University grant [1671/UN20.2.1/PG/2025]\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eData availability \u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eAll relevant data generated or analyzed during the work are included in this paper and any additional data can be made available upon reasonable request.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConflict of interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eThe authors declare that they have no conflict of interest.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eConsent to Publish\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eEthics Approval and Consent to Participate\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eNot applicable.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eJacoby Morris K, et al. 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Eur J Clin Invest. 2018;48:6. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1111/eci.12931\u003c/span\u003e\u003cspan address=\"10.1111/eci.12931\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e.\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Density functional theory (DFT), Time-dependent density functional theory (TDDFT), Computational spectroscopy, Systematic literature review","lastPublishedDoi":"10.21203/rs.3.rs-8815313/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8815313/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eDensity functional theory and time-dependent density functional theory are commonly used to interpret and predict spectroscopic properties of molecular and materials systems. However, a significant portion of TDDFT-based spectroscopic investigations still use isolated-molecule\u0026ensp; approximations that cannot reproduce the decisive role that realistic environments often play. In this comprehensive literature review, we recapitulate recent advances in environment-resolved DFT/TDDFT spectroscopy, with particular focus on\u0026ensp; the contributions of solvation, molecular aggregation, and interfacial electric fields to spectral signatures and charge-transfer mechanisms. In accordance with a PRISMA-style review design, the analysis of 83 peer-reviewed studies generated\u0026ensp; from all major application areas (such as molecular chromophores, fluorescent sensors, photoactive materials, supramolecular assemblies, nanoclusters, and hybrid interfaces). The findings emphasize that environmental interactions are not secondary perturbations but profoundly influence the excited-state electronic structure, often leading\u0026ensp; to qualitative changes in spectral features and mechanistic insights. Key studies in the surveyed literature consistently\u0026ensp; indicate that explicit microsolvation, aggregation modeling, and interface- and field-resolved methods improve spectroscopic fidelity to isolated-molecule models. This review lays out a comprehensive framework for environment-resolved computational spectroscopy and highlights many methodological gaps, e.g., disparate validation and the lack of consideration\u0026ensp; of collective and interfacial effects. In this paper, we aim to advance DFT/TDDFT spectroscopy toward predictive reliability and quantitative accuracy for complex molecular and materials systems by outlining best-practice recommendations and future research directions.\u003c/p\u003e","manuscriptTitle":"Beyond Isolated-Molecule TDDFT: Solvation, Aggregation, and Interfacial Fields in Predicting Spectroscopic Signatures and Charge-Transfer Mechanisms – A Systematic Review","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-03-04 17:04:16","doi":"10.21203/rs.3.rs-8815313/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"45b89dd8-2cf6-490b-a3cb-a44f31cf8b09","owner":[],"postedDate":"March 4th, 2026","published":true,"recentEditorialEvents":[{"type":"decision","content":"Rejected","date":"2026-05-11T13:19:11+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-05T08:20:54+00:00","index":57,"fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-05-04T05:57:15+00:00","index":56,"fulltext":""}],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2026-05-11T13:29:33+00:00","versionOfRecord":[],"versionCreatedAt":"2026-03-04 17:04:16","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8815313","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8815313","identity":"rs-8815313","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}