Coupling electrons and vibrations in molecular quantum chemistry

Dresselhaus, Thomas, Bungey, Callum B. A., Knowles, Peter J. ORCID: https://orcid.org/0000-0003-4657-6331 and Manby, Frederick R. 2020. Coupling electrons and vibrations in molecular quantum chemistry. The Journal of Chemical Physics 153 (21) , 214114. 10.1063/5.0032900

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Abstract

We derive an electron–vibration model Hamiltonian in a quantum chemical framework and explore the extent to which such a Hamiltonian can capture key effects of nonadiabatic dynamics. The model Hamiltonian is a simple two-body operator, and we make preliminary steps at applying standard quantum chemical methods to evaluate its properties, including mean-field theory, linear response, and a primitive correlated model. The Hamiltonian can be compared to standard vibronic Hamiltonians, but it is constructed without reference to potential energy surfaces through direct differentiation of the one- and two-electron integrals at a single reference geometry. The nature of the model Hamiltonian in the harmonic and linear-coupling regime is investigated for pyrazine, where a simple time-dependent calculation including electron–vibration correlation is demonstrated to exhibit the well-studied population transfer between the S2 and S1 excited states.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Chemistry Advanced Research Computing @ Cardiff (ARCCA)
Publisher:	American Institute of Physics
ISSN:	0021-9606
Funders:	EPSRC
Date of First Compliant Deposit:	10 December 2020
Date of Acceptance:	12 November 2020
Last Modified:	24 Nov 2024 14:00
URI:	https://orca.cardiff.ac.uk/id/eprint/136939

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