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Coupling electrons and vibrations in molecular quantum chemistry

Dresselhaus, Thomas, Bungey, Callum B. A., Knowles, Peter J. 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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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: 23 May 2022 17:05

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