Comparison of moving and fixed basis sets for nonadiabatic quantum dynamics at conical intersections
Please always quote using this URN: urn:nbn:de:bvb:20-opus-198699
- We assess the performance of two different types of basis sets for nonadiabatic quantum dynamics at conical intersections. The basis sets of both types are generated using Ehrenfest trajectories of nuclear coherent states. These trajectories can either serve as a moving (time-dependent) basis or be employed to sample a fixed (time-independent) basis. We demonstrate on the example of two-state two-dimensional and three-state five-dimensional models that both basis set types can yield highly accurate results for population transfer atWe assess the performance of two different types of basis sets for nonadiabatic quantum dynamics at conical intersections. The basis sets of both types are generated using Ehrenfest trajectories of nuclear coherent states. These trajectories can either serve as a moving (time-dependent) basis or be employed to sample a fixed (time-independent) basis. We demonstrate on the example of two-state two-dimensional and three-state five-dimensional models that both basis set types can yield highly accurate results for population transfer at intersections, as compared with reference quantum dynamics. The details of wave packet evolutions are discussed for the case of the two-dimensional model. The fixed basis is found to be superior to the moving one in reproducing true nonlocal spreading and maintaining correct shape of the wave packet upon time evolution. Moreover, for the models considered, the fixed basis set outperforms the moving one in terms of computational efficiency.…
Author: | Evgenii Titov, Alexander Humeniuk, Roland Mitric |
---|---|
URN: | urn:nbn:de:bvb:20-opus-198699 |
Document Type: | Preprint |
Faculties: | Fakultät für Chemie und Pharmazie / Institut für Physikalische und Theoretische Chemie |
Language: | English |
Parent Title (English): | Chemical Physics |
Year of Completion: | 2020 |
Source: | Chemical Physics, 528 (2020), 110526. https://doi.org/10.1016/j.chemphys.2019.110526 |
URL: | https://doi.org/10.1016/j.chemphys.2019.110526 |
Dewey Decimal Classification: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 541 Physikalische Chemie |
Tag: | Nonadiabatic quantum dynamics |
Release Date: | 2020/01/29 |
Embargo Date: | 2022/01/01 |
EU-Project number / Contract (GA) number: | 646737 |
OpenAIRE: | OpenAIRE |
Note: | Accepted manuscript |
Licence (German): | CC BY-NC-ND: Creative-Commons-Lizenz: Namensnennung, Nicht kommerziell, Keine Bearbeitungen 4.0 International |