Wavepacket dynamical study of H-atom tunneling in catecholate monoanion: the role of intermode couplings and energy flow

Bhattacharyya, D and Ramesh, SG (2022) Wavepacket dynamical study of H-atom tunneling in catecholate monoanion: the role of intermode couplings and energy flow. In: Physical Chemistry Chemical Physics .

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Abstract

We present a study of H-atom tunneling in catecholate monoanion through wavepacket dynamical simulations. In our earlier study of this symmetrical double-well system Phys. Chem. Chem. Phys., 2022, 24, 10887, a limited number of transition state modes were identified as being important for the tunneling process. These include the imaginary frequency mode Q1, the CO scissor mode Q10, and the OHO bending mode Q29. In this work, starting from non-stationary initial states prepared with excitations in these modes, we have carried out wavepacket dynamics in two and three dimensional spaces. We analyse the dynamical effects of the intermode couplings, in particular the role of energy flow between the studied modes on H-atom tunneling. We find that while Q10 strongly modulates the donor-acceptor distance, it does not exchange energy with Q1. However, excitation in Q29 or Q1 does lead to rapid energy exchange between these modes, which modifies the tunneling rate at early times. © 2023 The Royal Society of Chemistry.

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:	Couplings; Wave packets, Atom tunneling; Catecholate; Coupling flow; Double-well systems; Dynamical simulation; Energy flow; Intermode couplings; Monoanions; Transition state; Tunneling process, Atoms
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	31 Jan 2023 04:47
Last Modified:	31 Jan 2023 04:47
URI:	https://eprints.iisc.ac.in/id/eprint/79583

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