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Issue 7, 2014
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New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations

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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, 11ππ*, 11π3s/πσ* and 21ππ*. 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 11ππ* state with the GS in which the carbon-atom carrying the amino group is distorted out-of-plane. This suggests that excitation above the 11π3s/πσ* vertical excitation energy could be followed by electronic relaxation from the 11ππ* state to the ground-electronic state through this MECI. We find a MECI connecting the 11π3s/πσ* and 11ππ* states close to the local minimum on 11π3s/πσ* which suggests that photoexcitation to the 11π3s/πσ* state could be followed by relaxation to the 11ππ* state and to the dissociative component of the 11π3s/πσ* state. We also find evidence for a new pathway from the 21ππ* state to the ground electronic state that is likely to pass through a three-state conical intersection involving the 21ππ*, 11π3s/πσ* and 11ππ* states.

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

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Publication details

The article was received on 18 Oct 2013, accepted on 23 Dec 2013 and first published on 02 Jan 2014


Article type: Paper
DOI: 10.1039/C3CP54418D
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Citation: Phys. Chem. Chem. Phys., 2014,16, 3122-3133
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    New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations

    M. Sala, O. M. Kirkby, S. Guérin and H. H. Fielding, Phys. Chem. Chem. Phys., 2014, 16, 3122
    DOI: 10.1039/C3CP54418D

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