Coupling electrons and vibrations in molecular quantum chemistry

Research output: Contribution to journalArticle (Academic Journal)

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
JournalJournal of Chemical Physics
Publication statusAccepted/In press - 12 Nov 2020

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