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 |
Preview |
PDF
- Accepted Post-Print Version
Download (1MB) | Preview |
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: | 07 Nov 2023 14:45 |
URI: | https://orca.cardiff.ac.uk/id/eprint/136939 |
Citation Data
Cited 5 times in Scopus. View in Scopus. Powered By Scopus® Data
Actions (repository staff only)
Edit Item |