N-H photodissociation dynamics of electronically excited aniline: A three dimensional time-dependent quantum wavepacket study

Ray, J and Ramesh, SG (2021) N-H photodissociation dynamics of electronically excited aniline: A three dimensional time-dependent quantum wavepacket study. In: Physical Chemistry Chemical Physics, 23 (29). pp. 15727-15748.

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Abstract

We have simulated the dynamics of 1��� state-mediated nonadiabatic N-H bond dissociation in photo-excited aniline (C6H5NH2). A three electronic state diabatic model potential, involving the ground, 1���, and 1��� diabatic states, and focussing on the NH2 degrees of freedom alone is constructed using XMS-CASPT2 energies. Using a kinetic energy operator in the polyspherical framework, wavepacket dynamics in three vibrational modes, viz. NH stretch, NH2 out-of-plane wag and torsion, is carried out using the Chebyshev propagation scheme. For optically bright 1��� excitation, the wavepacket can access the 1���/1��� and 1��/1��� conical intersections that lie en route to dissociation. For both intersections, NH2 out-of-plane wag and torsional motions are the most dominant coupling coordinates. Carrying out dynamics with initial wavepackets varying in excitation in the three degrees of freedom, we probe their roles in the evolution of the state populations, probability densities, and product branching for the NH dissociation process. This journal is © the Owner Societies.

Item Type:	Journal Article
Publication:	Physical Chemistry Chemical Physics
Publisher:	Royal Society of Chemistry
Additional Information:	The copyright for this article belongs to Royal Society of Chemistry
Keywords:	Aniline; Degrees of freedom (mechanics); Kinetic energy; Kinetics; Photodissociation; Wave packets, Conical intersection; Dissociation process; Kinetic-energy operator; Photodissociation dynamics; Probability densities; Quantum wave packets; Three degrees of freedom; Wave-packet dynamics, Excited states
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	25 Sep 2021 13:34
Last Modified:	25 Sep 2021 13:34
URI:	http://eprints.iisc.ac.in/id/eprint/69807

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