Journal of Computational Chemistry, volume 41, issue 18, pages 1718-1729

How accurate are TD‐DFT excited‐state geometries compared to DFT ground‐state geometries?

Wang Jun ^{1, 2}

Durbeej Bo ¹

Hide authors affiliations Show authors affiliations: 2 affiliations

Division of Theoretical Chemistry, IFMLinköping University Linköping Sweden |

Institut de Química Computacional i Catàlisi, Facultat de CiènciesUniversitat de Girona Girona Spain |

Publication type: Journal Article

Publication date: 2020-04-23

Wiley

Journal: Journal of Computational Chemistry

Quartile SCImago

Quartile WOS

Impact factor: 3

ISSN: 01928651, 1096987X

DOI: 10.1002/jcc.26213

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General Chemistry

Computational Mathematics

Abstract

In this work, we take a different angle to the benchmarking of time‐dependent density functional theory (TD‐DFT) for the calculation of excited‐state geometries by extensively assessing how accurate such geometries are compared to ground‐state geometries calculated with ordinary DFT. To this end, we consider 20 medium‐sized aromatic organic compounds whose lowest singlet excited states are ideally suited for TD‐DFT modeling and are very well described by the approximate coupled‐cluster singles and doubles (CC2) method, and then use this method and six different density functionals (BP86, B3LYP, PBE0, M06‐2X, CAM‐B3LYP, and ωB97XD) to optimize the corresponding ground‐ and excited‐state geometries. The results show that although each hybrid functional reproduces the CC2 excited‐state bond lengths very satisfactorily, achieving an overall root mean square error of 0.011 Å for all 336 bonds in the 20 molecules, these errors are distinctly larger than those of only 0.004–0.006 Å with which the hybrid functionals reproduce the CC2 ground‐state bond lengths. Furthermore, for each functional employed, the variation in the error relative to CC2 between different molecules is found to be much larger (by at least a factor of 3) for the excited‐state geometries than for the ground‐state geometries, despite the fact that the molecules/states under investigation have rather uniform chemical and spectroscopic character. Overall, the study finds that even in favorable circumstances, TD‐DFT excited‐state geometries appear intrinsically and comparatively less accurate than DFT ground‐state ones.

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Citations by journals

	1 2 3 4 5
Journal of Physical Chemistry A	Journal of Physical Chemistry A, 5, 8.77% Journal of Physical Chemistry A 5 publications, 8.77%
Physical Chemistry Chemical Physics	Physical Chemistry Chemical Physics, 5, 8.77% Physical Chemistry Chemical Physics 5 publications, 8.77%
Journal of Molecular Structure	Journal of Molecular Structure, 4, 7.02% Journal of Molecular Structure 4 publications, 7.02%
Molecules	Molecules, 3, 5.26% Molecules 3 publications, 5.26%
Journal of Chemical Physics	Journal of Chemical Physics, 3, 5.26% Journal of Chemical Physics 3 publications, 5.26%
Journal of Chemical Theory and Computation	Journal of Chemical Theory and Computation, 3, 5.26% Journal of Chemical Theory and Computation 3 publications, 5.26%
International Journal of Molecular Sciences	International Journal of Molecular Sciences, 2, 3.51% International Journal of Molecular Sciences 2 publications, 3.51%
Computational and Theoretical Chemistry	Computational and Theoretical Chemistry, 2, 3.51% Computational and Theoretical Chemistry 2 publications, 3.51%
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy	Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2, 3.51% Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy 2 publications, 3.51%
Journal of Materials Chemistry C	Journal of Materials Chemistry C, 2, 3.51% Journal of Materials Chemistry C 2 publications, 3.51%
Journal of Organic Chemistry	Journal of Organic Chemistry, 1, 1.75% Journal of Organic Chemistry 1 publication, 1.75%
Physical Review A	Physical Review A, 1, 1.75% Physical Review A 1 publication, 1.75%
Chemosensors	Chemosensors, 1, 1.75% Chemosensors 1 publication, 1.75%
Results in Chemistry	Results in Chemistry, 1, 1.75% Results in Chemistry 1 publication, 1.75%
Journal of Photochemistry and Photobiology A: Chemistry	Journal of Photochemistry and Photobiology A: Chemistry, 1, 1.75% Journal of Photochemistry and Photobiology A: Chemistry 1 publication, 1.75%
Journal of Physics and Chemistry of Solids	Journal of Physics and Chemistry of Solids, 1, 1.75% Journal of Physics and Chemistry of Solids 1 publication, 1.75%
Organic Materials	Organic Materials, 1, 1.75% Organic Materials 1 publication, 1.75%
Chemical Physics	Chemical Physics, 1, 1.75% Chemical Physics 1 publication, 1.75%
Small	Small, 1, 1.75% Small 1 publication, 1.75%
ChemPhotoChem	ChemPhotoChem, 1, 1.75% ChemPhotoChem 1 publication, 1.75%
Journal of Computational Chemistry	Journal of Computational Chemistry, 1, 1.75% Journal of Computational Chemistry 1 publication, 1.75%
Bulletin of the Korean Chemical Society	Bulletin of the Korean Chemical Society, 1, 1.75% Bulletin of the Korean Chemical Society 1 publication, 1.75%
ACS Nano	ACS Nano, 1, 1.75% ACS Nano 1 publication, 1.75%
JACS Au	JACS Au, 1, 1.75% JACS Au 1 publication, 1.75%
Journal of Chemical Information and Modeling	Journal of Chemical Information and Modeling, 1, 1.75% Journal of Chemical Information and Modeling 1 publication, 1.75%
Journal of Physical Chemistry B	Journal of Physical Chemistry B, 1, 1.75% Journal of Physical Chemistry B 1 publication, 1.75%
Journal of Physical Chemistry C	Journal of Physical Chemistry C, 1, 1.75% Journal of Physical Chemistry C 1 publication, 1.75%
Materials Chemistry Frontiers	Materials Chemistry Frontiers, 1, 1.75% Materials Chemistry Frontiers 1 publication, 1.75%
Phase Transitions	Phase Transitions, 1, 1.75% Phase Transitions 1 publication, 1.75%
Journal of Spectroscopy	Journal of Spectroscopy, 1, 1.75% Journal of Spectroscopy 1 publication, 1.75%
	1 2 3 4 5

Citations by publishers

	2 4 6 8 10 12 14
American Chemical Society (ACS)	American Chemical Society (ACS), 14, 24.56% American Chemical Society (ACS) 14 publications, 24.56%
Elsevier	Elsevier, 14, 24.56% Elsevier 14 publications, 24.56%
Royal Society of Chemistry (RSC)	Royal Society of Chemistry (RSC), 8, 14.04% Royal Society of Chemistry (RSC) 8 publications, 14.04%
Multidisciplinary Digital Publishing Institute (MDPI)	Multidisciplinary Digital Publishing Institute (MDPI), 7, 12.28% Multidisciplinary Digital Publishing Institute (MDPI) 7 publications, 12.28%
Wiley	Wiley, 4, 7.02% Wiley 4 publications, 7.02%
American Institute of Physics (AIP)	American Institute of Physics (AIP), 3, 5.26% American Institute of Physics (AIP) 3 publications, 5.26%
American Physical Society (APS)	American Physical Society (APS), 1, 1.75% American Physical Society (APS) 1 publication, 1.75%
Thieme	Thieme, 1, 1.75% Thieme 1 publication, 1.75%
Taylor & Francis	Taylor & Francis, 1, 1.75% Taylor & Francis 1 publication, 1.75%
Hindawi Limited	Hindawi Limited, 1, 1.75% Hindawi Limited 1 publication, 1.75%
IOP Publishing	IOP Publishing, 1, 1.75% IOP Publishing 1 publication, 1.75%
Canadian Science Publishing	Canadian Science Publishing, 1, 1.75% Canadian Science Publishing 1 publication, 1.75%
	2 4 6 8 10 12 14

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Wang J., Durbeej B. How accurate are TD‐DFT excited‐state geometries compared to DFT ground‐state geometries? // Journal of Computational Chemistry. 2020. Vol. 41. No. 18. pp. 1718-1729.

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Wang J., Durbeej B. How accurate are TD‐DFT excited‐state geometries compared to DFT ground‐state geometries? // Journal of Computational Chemistry. 2020. Vol. 41. No. 18. pp. 1718-1729.

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