Analytic non-adiabatic derivative coupling terms for spin-orbit MRCI wavefunctions. I. Formalism.

Analytic gradients of electronic eigenvalues require one calculation per nuclear geometry, compared to at least 3n + 1 calculations for finite difference methods, where n is the number of nuclei. Analytic nonadiabatic derivative coupling terms (DCTs), which are calculated in a similar fashion, are used to remove nondiagonal contributions to the kinetic energy operator, leading to more accurate nuclear dynamics calculations than those that employ the Born-Oppenheimer approximation, i.e., that assume off-diagonal contributions are zero. The current methods and underpinnings for calculating both of these quantities, gradients and DCTs, for the State-Averaged MultiReference Configuration Interaction with Singles and Doubles (MRCI-SD) wavefunctions in COLUMBUS are reviewed. Before this work, these methods were not available for wavefunctions of a relativistic MRCI-SD Hamiltonian. Calculation of these terms is critical in successfully modeling the dynamics of systems that depend on transitions between potential energy surfaces split by the spin-orbit operator, such as diode-pumped alkali lasers. A formalism for calculating the transition density matrices and analytic derivative coupling terms for such systems is presented.