Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method

0500250 - ÚFCH JH 2019 RIV US eng J - Journal Article
Hollas, D. - Šištík, L. - Hohenstein, E. G. - Martínez, T. J. - Slavíček, Petr
Nonadiabatic Ab Initio Molecular Dynamics with the Floating Occupation Molecular Orbital-Complete Active Space Configuration Interaction Method.
Journal of Chemical Theory and Computation. Roč. 14, č. 1 (2018), s. 339-350. ISSN 1549-9618. E-ISSN 1549-9626
Grant - others:GA ČR(CZ) GA13-34168S
Institutional support: RVO:61388955
Keywords : quantum chemistry * ethylene * density-functional theory
OECD category: Physical chemistry
Impact factor: 5.313, year: 2018

We show that the floating occupation molecular orbital complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the widely used complete active space self-consistent field (CASSCF) method in direct nonadiabatic dynamics simulations. We have simulated photodynamics of three archetypal molecules in photodynamics: ethylene, methaniminium cation, and malonaldehyde. We compared the time evolution of electronic populations and reaction mechanisms as revealed by the FOMO-CASCI and CASSCF approaches. Generally, the two approaches provide similar results. Some dynamical differences are observed, but these can be traced back to energetically minor differences in the potential energy surfaces. We suggest that the FOMO-CASCI method represents, due to its efficiency and stability, a promising approach for direct ab initio dynamics in the excited state.
Permanent Link: http://hdl.handle.net/11104/0292351