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Interstate vibronic coupling constants between electronic excited states for complex molecules

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journal contribution
posted on 04.04.2018 by Maria Fumanal, Felix Plasser, Sebastian Mai, Chantal Daniel, Etienne Gindensperger
In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)3(N,N)(L)]n+ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.

Funding

M.F., C.D., and E.G. acknowledge funding from the Agence Nationale de la Recherche within Project Nos. ANR-10-LABX-0026 (Chimie des Systemes Complexes) and ANR-15-CE29-0027-01 (DeNeTheor) as well as the Frontier Research in Chemistry Foundation, Strasbourg. F.P. and S.M. acknowledge funding from the Austrian Science Fund (FWF) within Project No. I2883 (DeNeTheor) and the University of Vienna, as well as the Vienna Scientific Cluster (VSC) for generous allocation of computing time. Support from the COST action CM1305 (ECostBio) is acknowledged.

History

School

  • Science

Department

  • Chemistry

Published in

Journal of Chemical Physics

Citation

FUMANAL, M. ... et al, 2018. Interstate vibronic coupling constants between electronic excited states for complex molecules. The Journal of Chemical Physics, 148 (12), 124119.

Publisher

AIP Publishing © The Authors

Version

AM (Accepted Manuscript)

Publisher statement

This work is made available according to the conditions of the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0) licence. Full details of this licence are available at: https://creativecommons.org/licenses/by-nc-nd/4.0/

Acceptance date

23/02/2018

Publication date

2018-03-29

Notes

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. The following article appeared in FUMANAL, M. ... et al, 2018. Interstate vibronic coupling constants between electronic excited states for complex molecules. The Journal of Chemical Physics, 148 (12), 124119 and may be found at https://doi.org/10.1063/1.5022760.

ISSN

0021-9606

eISSN

1089-7690

Language

en

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