Coupling electrons and vibrations in molecular quantum chemistry

Thomas Dresselhaus, Callum B A Bungey, Peter J. Knowles, Frederick R Manby*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

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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 evaluating its properties, including mean-field theory, linear response, and a primitive correlated model. The Hamiltonian can be compared to standard vibronic Hamiltonians, but 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.
Original languageEnglish
Article number214114
Number of pages14
JournalJournal of Chemical Physics
Volume153
Early online date4 Dec 2020
DOIs
Publication statusE-pub ahead of print - 4 Dec 2020

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