Hohenstein, Edward G.Bouduban, Marine E. F.Song, ChenchenLuehr, NathanUfimtsev, Ivan S.Martinez, Todd J.2015-09-282015-09-282015-09-28201510.1063/1.4923259https://infoscience.epfl.ch/handle/20.500.14299/118950WOS:000357873900015The floating occupation molecular orbital-complete active space configuration interaction (FOMO-CASCI) method is a promising alternative to the state-averaged complete active space self-consistent field (SA-CASSCF) method. We have formulated the analytic first derivative of FOMO-CASCI in a manner that is well-suited for a highly efficient implementation using graphical processing units (GPUs). Using this implementation, we demonstrate that FOMO-CASCI gradients are of similar computational expense to configuration interaction singles (CIS) or time-dependent density functional theory (TDDFT). In contrast to CIS and TDDFT, FOMO-CASCI can describe multireference character of the electronic wavefunction. We show that FOMO-CASCI compares very favorably to SA-CASSCF in its ability to describe molecular geometries and potential energy surfaces around minimum energy conical intersections. Finally, we apply FOMO-CASCI to the excited state hydrogen transfer reaction in methyl salicylate. (C) 2015 AIP Publishing LLC.text::journal::journal article::research article