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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.
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 language | English |
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Article number | 214114 |
Number of pages | 14 |
Journal | Journal of Chemical Physics |
Volume | 153 |
Early online date | 4 Dec 2020 |
DOIs | |
Publication status | E-pub ahead of print - 4 Dec 2020 |
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Dive into the research topics of 'Coupling electrons and vibrations in molecular quantum chemistry'. Together they form a unique fingerprint.Projects
- 1 Finished
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A unified framework for quantum chemistry beyond the Born-Oppenheimer approximation
Manby, F. R. (Principal Investigator)
1/05/18 → 30/04/22
Project: Research