Molecular dynamics in electronically excited states using time-dependent density functional theory

Détails

ID Serval
serval:BIB_2D250765C9B3
Type
Article: article d'un périodique ou d'un magazine.
Collection
Publications
Titre
Molecular dynamics in electronically excited states using time-dependent density functional theory
Périodique
Molecular Physics
Auteur(s)
Tavernelli I., Röhrig U.F., Rothlisberger U.
ISSN
1362-3028 (Electronic)
ISSN-L
0026-8976 (Print)
Statut éditorial
Publié
Date de publication
2005
Peer-reviewed
Oui
Volume
103
Numéro
6-8
Pages
963-981
Langue
anglais
Résumé
We describe two different implementations of time-dependent density functional theory (TDDFT) for use in excited state molecular dynamics simulations. One is based on the linear response formulation (LR-TDDFT), whereas the other uses a time propagation scheme for the electronic wave functions (P-TDDFT). Photo-induced cis-trans isomerization of C=C, C=N and N=N double bonds is investigated in three model compounds, namely the 2,4-pentadiene-1-iminium cation (PSB), formaldimine and diimide. For formaldimine and diimide, the results obtained with both schemes are in agreement with experimental data and previously reported theoretical results. Molecular dynamics simulations yield new insights into the relaxation pathways in the excited state. For PSB, which is a model system for the retinal protonated Schiff base involved in the Visual process, the forces computed from the LR-TDDFT S-1 surface lead to an increased bond length alternation and, consequently, to single bond rotation. On the contrary, P-TDDFT dynamics lead to a decreased bond length alternation, in agreement with CASPT2 and restricted open-shell Kohn-Sham (ROKS) calculations.
Web of science
Création de la notice
30/10/2015 9:09
Dernière modification de la notice
20/08/2019 13:12
Données d'usage