Electronic excitations in molecular solids: bridging theory and experiment

Jonathan M. Skelton, E. Lora Da Silva, Rachel Crespo-Otero, Lauren E. Hatcher, Paul R. Raithby, Stephen C. Parker, Aron Walsh

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Abstract

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 (e.g. 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(Et4dien)(η2-O,ON)(η1- NO2)] 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.
Original languageEnglish
Pages (from-to)181-202
Number of pages21
JournalFaraday Discussions
Volume177
Early online date29 Jan 2015
DOIs
Publication statusPublished - 1 Apr 2015

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Molecular crystals
electronics
excitation
Experiments
Computational chemistry
computational chemistry
Photochemical reactions
Isomerization
temporal resolution
Excited states
linkages
Isomers
photochemical reactions
isomerization
crystals
isomers
spatial resolution
Crystalline materials
solid state
approximation

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Electronic excitations in molecular solids : bridging theory and experiment. / Skelton, Jonathan M.; Da Silva, E. Lora; Crespo-Otero, Rachel; Hatcher, Lauren E.; Raithby, Paul R.; Parker, Stephen C.; Walsh, Aron.

In: Faraday Discussions, Vol. 177, 01.04.2015, p. 181-202.

Research output: Contribution to journalArticle

Skelton, JM, Da Silva, EL, Crespo-Otero, R, Hatcher, LE, Raithby, PR, Parker, SC & Walsh, A 2015, 'Electronic excitations in molecular solids: bridging theory and experiment', Faraday Discussions, vol. 177, pp. 181-202. https://doi.org/10.1039/C4FD00168K
Skelton, Jonathan M. ; Da Silva, E. Lora ; Crespo-Otero, Rachel ; Hatcher, Lauren E. ; Raithby, Paul R. ; Parker, Stephen C. ; Walsh, Aron. / Electronic excitations in molecular solids : bridging theory and experiment. In: Faraday Discussions. 2015 ; Vol. 177. pp. 181-202.
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