Nonadiabatic Forward Flux Sampling for Excited-State Rare Events
- Author(s)
- Madlen Maria Reiner, Brigitta Bachmair, Maximilian Xaver Tiefenbacher, Sebastian Mai, Leticia González, Philipp Marquetand, Christoph Dellago
- Abstract
We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory surface hopping (TSH) method for nonadiabatic dynamics. NAFFS is applied to two dynamically relevant excited-state models that feature an avoided crossing and a conical intersection with tunable parameters. We investigate how nonadiabatic couplings, temperature, and reaction barriers affect transition rate constants in regimes that cannot be otherwise obtained with plain, traditional TSH. The comparison with reference brute-force TSH simulations for limiting cases of rareness shows that NAFFS can be several orders of magnitude cheaper than conventional TSH and thus represents a conceptually novel tool to extend excited-state dynamics to time scales that are able to capture rare nonadiabatic events.
- Organisation(s)
- Research Platform Accelerating Photoreaction Discovery, Department of Theoretical Chemistry, Computational and Soft Matter Physics
- Journal
- Journal of Chemical Theory and Computation
- Volume
- 19
- Pages
- 1657–1671
- No. of pages
- 15
- ISSN
- 1549-9618
- DOI
- https://doi.org/10.1021/acs.jctc.2c01088
- Publication date
- 03-2023
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103006 Chemical physics, 104022 Theoretical chemistry, 102009 Computer simulation
- ASJC Scopus subject areas
- Computer Science Applications, Physical and Theoretical Chemistry
- Portal url
- https://ucris.univie.ac.at/portal/en/publications/nonadiabatic-forward-flux-sampling-for-excitedstate-rare-events(31ef9c40-c406-4e4b-b6a5-eebd69a77314).html