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Lookup NU author(s): Dr Julien EngORCiD, Professor Thomas Penfold
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
Excited state dynamics play a critical role across a broad range of scientific fields. Importantly, the highly non-equilibrium nature of the states generated by photoexcitation means that excited state simulations should usually include an accurate description of the coupled electronic-nuclear motion, which often requires solving the time-dependent Schrödinger equation (TDSE). One of the biggest challenges for these simulations is the requirement to calculate the PES over which the nuclei evolve. An effective approach for addressing this challenge is to use the approximate linear vibronic coupling (LVC) Hamiltonian, which enables a model potential to be parameterised using relatively few quantum chemistry calculations. However, this approach is only valid provided there are no large amplitude motions in the excited state dynamics. In this paper we introduce and deploy a metric, the Global Anharmonicity Parameter (GAP), which can used to assess the accuracy of an LVC potential. Following its derivation, we illustrate its utility by applying it to three molecules exhibiting different rigidity in their excited states.
Author(s): Eng J, Penfold TJ
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Year: 2023
Volume: 25
Issue: 10
Pages: 7195-7204
Online publication date: 09/02/2023
Acceptance date: 08/02/2023
Date deposited: 09/02/2023
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
URL: https://doi.org/10.1039/D2CP05576G
DOI: 10.1039/D2CP05576G
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