Nonadiabatic Forward Flux Sampling for Excited-State Rare Events

Autor(en)

Madlen Maria Reiner, Brigitta Bachmair, Maximilian Xaver Tiefenbacher, Sebastian Mai, Leticia González, Philipp Marquetand, Christoph Dellago

Abstrakt

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(en)

Forschungsplattform Accelerating Photoreaction Discovery, Institut für Theoretische Chemie, Computergestützte Physik und Physik der Weichen Materie

Journal

Journal of Chemical Theory and Computation

Band

19

Seiten

1657–1671

Anzahl der Seiten

15

ISSN

1549-9618

DOI

https://doi.org/10.1021/acs.jctc.2c01088

Publikationsdatum

03-2023

Peer-reviewed

Ja

ÖFOS 2012

103006 Chemische Physik, 104022 Theoretische Chemie, 102009 Computersimulation

ASJC Scopus Sachgebiete

Computer Science Applications, Physical and Theoretical Chemistry

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/31ef9c40-c406-4e4b-b6a5-eebd69a77314