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.

Department of Chemistry and Biochemistry The City College of New York New York New York 10031 United States

Department of Chemistry and the PULSE Institute Stanford University Stanford California 94305 United States

Department of Physical Chemistry University of Chemistry and Technology Prague Technická 5 16628 Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry Dolejškova 3 18223 Prague 8 Czech Republic

PhD Program in Chemistry The Graduate Center of the City University of New York New York New York 10016 United States

SLAC National Accelerator Laboratory Menlo Park California 94025 United States

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