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New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations.

Sala, M; Kirkby, OM; Guérin, S; Fielding, HH; (2014) New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations. Phys Chem Chem Phys , 16 (7) 3122 - 3133. 10.1039/c3cp54418d. Green open access

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Abstract

There have been a number of recent experimental investigations of the nonadiabatic relaxation dynamics of aniline following excitation to the first three singlet excited states, 1(1)ππ*, 1(1)π3s/πσ* and 2(1)ππ*. Motivated by differences between the interpretations of experimental observations, we have employed CASSCF and XMCQDPT2 calculations to explore the potential energy landscape and relaxation pathways of photoexcited aniline. We find a new prefulvene-like MECI connecting the 1(1)ππ* state with the GS in which the carbon-atom carrying the amino group is distorted out-of-plane. This suggests that excitation above the 1(1)π3s/πσ* vertical excitation energy could be followed by electronic relaxation from the 1(1)ππ* state to the ground-electronic state through this MECI. We find a MECI connecting the 1(1)π3s/πσ* and 1(1)ππ* states close to the local minimum on 1(1)π3s/πσ* which suggests that photoexcitation to the 1(1)π3s/πσ* state could be followed by relaxation to the 1(1)ππ* state and to the dissociative component of the 1(1)π3s/πσ* state. We also find evidence for a new pathway from the 2(1)ππ* state to the ground electronic state that is likely to pass through a three-state conical intersection involving the 2(1)ππ*, 1(1)π3s/πσ* and 1(1)ππ* states.

Type: Article
Title: New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations.
Location: England
Open access status: An open access version is available from UCL Discovery
DOI: 10.1039/c3cp54418d
Publisher version: http://dx.doi.org/10.1039/c3cp54418d
Language: English
Additional information: This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
UCL classification: UCL
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/1452185
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