{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,13]],"date-time":"2025-10-13T19:56:24Z","timestamp":1760385384464,"version":"3.37.3"},"reference-count":70,"publisher":"Royal Society of Chemistry (RSC)","funder":[{"name":"European Research Council","award":["277757"],"award-info":[{"award-number":["277757"]}]}],"content-domain":{"domain":["rsc.org"],"crossmark-restriction":true},"short-container-title":["Faraday Discuss."],"abstract":"<p>As the spatial and temporal resolution accessible to experiment and theory converge, computational chemistry is an increasingly powerful tool for modelling and interpreting spectroscopic data. However, the study of molecular processes, in particular those related to electronic excitations (<italic>e.g.<\/italic> photochemistry), frequently pushes quantum-chemical techniques to their limit. The disparity in the level of theory accessible to periodic and molecular calculations presents a significant challenge when modelling molecular crystals, since accurate calculations require a high level of theory to describe the molecular species, but must also take into account the influence of the crystalline environment on their properties. In this article, we briefly review the different classes of quantum-chemical techniques, and present an overview of methods that account for environmental influences with varying levels of approximation. Using a combination of solid-state and molecular calculations, we quantitatively evaluate the performance of implicit-solvent models for the [Ni(Et<sub>4<\/sub>dien)(\u03b7<sup>2<\/sup>-O,ON)(\u03b7<sup>1<\/sup>-NO<sub>2<\/sub>)] linkage-isomer system as a test case. We focus particularly on the accurate reproduction of the energetics of the isomerisation, and on predicting spectroscopic properties to compare with experimental results. This work illustrates how the synergy between periodic and molecular calculations can be exploited for the study of molecular crystals, and forms a basis for the investigation of more challenging phenomena, such as excited-state dynamics, and for further methodological developments.<\/p>","DOI":"10.1039\/c4fd00168k","type":"journal-article","created":{"date-parts":[[2014,10,22]],"date-time":"2014-10-22T10:01:15Z","timestamp":1413972075000},"page":"181-202","update-policy":"https:\/\/doi.org\/10.1039\/rsc_crossmark_policy","source":"Crossref","is-referenced-by-count":11,"title":["Electronic excitations in molecular solids: bridging theory and experiment"],"prefix":"10.1039","volume":"177","author":[{"given":"Jonathan M.","family":"Skelton","sequence":"first","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"E.","family":"Lora da Silva","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"Rachel","family":"Crespo-Otero","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"Lauren E.","family":"Hatcher","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"Paul R.","family":"Raithby","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"Stephen C.","family":"Parker","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]},{"given":"Aron","family":"Walsh","sequence":"additional","affiliation":[{"name":"Department of Chemistry"},{"name":"University of Bath"},{"name":"Bath"},{"name":"UK"}]}],"member":"292","published-online":{"date-parts":[[2015]]},"reference":[{"key":"C4FD00168K-(cit1)\/*[position()=1]","volume-title":"Jacob\u2019s ladder of density functional approximations for the exchange-correlation energy","author":"Perdew","year":"2001","unstructured":"J. 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This article is licensed under a Creative Commons Attribution 3.0 Unported Licence (CC BY 3.0)","URL":"http:\/\/creativecommons.org\/licenses\/by\/3.0\/","name":"copyright_licence","label":"OPEN ACCESS","group":{"name":"copyright_licensing","label":"COPYRIGHT AND LICENSING"}},{"value":"Single-blind","order":2,"name":"peer_review_method","group":{"name":"peer_review_method","label":"PEER REVIEW METHOD"}},{"value":"Received 5 September 2014; Accepted 22 October 2014;  Advance Article published 29 January 2015;  Version of Record published 11 April 2015","order":1,"name":"history","group":{"name":"publication_history","label":"PUBLICATION HISTORY"}}]}}