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  5. Accurate and efficient computation of optical absorption spectra of molecular crystals: the case of the polymorphs of ROY
 
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Accurate and efficient computation of optical absorption spectra of
molecular crystals: the case of the polymorphs of ROY
File(s)
jcap_ROY_accepted_arxiv-2103.11732.pdf (1.68 MB)
Accepted version
Author(s)
Prentice, Joseph
Mostofi, Arash A
Type
Journal Article
Abstract
When calculating the optical absorption spectra of molecular crystals from first principles, the influence of the crystalline environment on the excitations is of significant importance. For such systems, however, methods to describe the excitations accurately can be computationally prohibitive due to the relatively large system sizes involved. In this work, we demonstrate a method that allows optical absorption spectra to be computed both efficiently and at high accuracy. Our approach is based on the spectral warping method successfully applied to molecules in solvent. It involves calculating the absorption spectrum of a supercell of the full molecular crystal using semi-local time-dependent density functional theory (TDDFT), before warping the spectrum using a transformation derived from smaller-scale semi-local and hybrid TDDFT calculations on isolated dimers. We demonstrate the power of this method on three polymorphs of the well-known color polymorphic compound ROY and find that it outperforms both small-scale hybrid TDDFT dimer calculations and large-scale semi-local TDDFT supercell calculations, when compared to the experiment.
Date Issued
2021-08-10
Date Acceptance
2021-07-06
Citation
Journal of Chemical Theory and Computation, 2021, 17 (8), pp.5214-5224
URI
http://hdl.handle.net/10044/1/90812
URL
https://pubs.acs.org/doi/10.1021/acs.jctc.1c00227
DOI
https://www.dx.doi.org/10.1021/acs.jctc.1c00227
ISSN
1549-9618
Publisher
American Chemical Society
Start Page
5214
End Page
5224
Journal / Book Title
Journal of Chemical Theory and Computation
Volume
17
Issue
8
Copyright Statement
© 2021 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Chemical Theory and Computation, after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jctc.1c00227
Sponsor
Engineering & Physical Science Research Council (E
Identifier
https://pubs.acs.org/doi/10.1021/acs.jctc.1c00227
Grant Number
EP/P02209X/1
Subjects
cond-mat.mtrl-sci
cond-mat.mtrl-sci
physics.comp-ph
Chemical Physics
0307 Theoretical and Computational Chemistry
0601 Biochemistry and Cell Biology
0803 Computer Software
Publication Status
Published
Date Publish Online
2021-07-22
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