Mind the GAP: quantifying the breakdown of the linear vibronic coupling Hamiltonian

Literature Information

Publication Date 2023-02-09
DOI 10.1039/D2CP05576G
Impact Factor 3.676
Authors

Thomas J Penfold, Julien Eng


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Abstract

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 be 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.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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