Excited-State Decay in the Photoisomerisation of Azobenzene: A New Balance between Mechanisms
File(s)Manuscript_MReguero-v2-changes.pdf (1.97 MB)
Accepted version
Author(s)
Casellas, J
Bearpark, MJ
Reguero, M
Type
Journal Article
Abstract
The mechanism of the photoisomerization of azobenzene has been studied by means of multiconfigurational ab initio calculations. Our results show that it is necessary to account for the dynamic electron correlation in the location of the critical points (CASPT2 optimizations) to obtain a correct description of the topography of the potential energy surfaces of the low-energy singlet excited states. Using this methodology, we have found that the state populated by the initial excitation is the S2 (ππ*) state, which decays very efficiently to the S1 (nπ*) state at a pedal-like non-rotated geometry. On the S1 state, relaxation leads to a rotated geometry where the system decays to the ground state, in which further relaxation can lead to either the trans or cis geometries. However the S1/S0 CI seam also extends to planar geometries, so this reaction path is also accessible for rotation-constrained systems. Our results explain the experimental observations satisfactorily.
Date Issued
2016-07-11
Date Acceptance
2016-07-01
Citation
Chemphyschem, 2016, 17 (19), pp.3068-3079
ISSN
1439-7641
Publisher
Wiley-VCH Verlag
Start Page
3068
End Page
3079
Journal / Book Title
Chemphyschem
Volume
17
Issue
19
Copyright Statement
© 2016 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim. This is the accepted version of the following article, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/cphc.201600502/abstract;jsessionid
Subjects
ab initio calculations
azo compounds
photoisomerisation
reaction mechanisms
Chemical Physics
Physical Chemistry (Incl. Structural)
Atomic, Molecular, Nuclear, Particle And Plasma Physics
Theoretical And Computational Chemistry
Publication Status
Published