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Conical intersections involving the lowest (1)pi sigma* state in aniline: Role of the NH2 group

Ray, Jyotirmoy and Ramesh, Sai G (2018) Conical intersections involving the lowest (1)pi sigma* state in aniline: Role of the NH2 group. In: CHEMICAL PHYSICS, 515 . pp. 77-87.

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Official URL: https://doi.org/10.1016/j.chemphys.2018.03.015


At low excitation energies of under 5 eV, conical intersections (CIs) involving the lowest three electronic states of aniline, viz. the (1)pi pi*/(1)pi sigma* and (1)pi sigma*/GS intersections, are accessible. Signatures of ultrafast dynamics, including H atom loss, are observed experimentally with energies above the (1)pi sigma* threshold. Ab initio results corroborate the view that the intersections are involved in the rapid population flow. In the present computational study, we characterize these intersections using the CASSCF and XMS-CASPT2 methods. We locate the CIs and analyse the important vibronic couplings at these geometries from a normal mode as well as an NH2 local mode perspective. Through our findings, we suggest that modes largely local to the NH2 group couple the electronic states the strongest at these intersections. (C) 2018 Elsevier B.V. All rights reserved.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to ELSEVIER SCIENCE BV
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 28 Jan 2019 09:37
Last Modified: 28 Jan 2019 09:37
URI: http://eprints.iisc.ac.in/id/eprint/61499

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