title: Analytic first derivatives of floating occupation molecular orbital-complete active space configuration interaction on graphical processing units.
abstract: The 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.
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Edward G
authors.initials: EG
authors.lastname: Hohenstein
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Marine E F
authors.initials: ME
authors.lastname: Bouduban
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Chenchen
authors.initials: C
authors.lastname: Song
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Nathan
authors.initials: N
authors.lastname: Luehr
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Ivan S
authors.initials: IS
authors.lastname: Ufimtsev
authors.affiliation: Department of Chemistry and the PULSE Institute, Stanford University, Stanford, California 94305, USA.
authors.forename: Todd J
authors.initials: TJ
authors.lastname: Martínez