Fast numerical evaluation of time-derivative nonadiabatic couplings for mixed quantum-classical methods

Abstract: We have developed a numerical differentiation scheme which eliminates evaluation of overlap determinants in calculating the time-derivative non-adiabatic couplings (TDNACs). Evaluation of these determinants was the bottleneck in previous implementations of mixed quantum-classical methods using numerical differentiation of electronic wave functions in the Slater-determinant representation. The central idea of our approach is, first, to reduce the analytic time derivatives of Slater determinants to time derivatives of molecular orbitals, and then to apply a finite-difference formula. Benchmark calculations prove the efficiency of the proposed scheme showing impressive several-order-of-magnitude speedups of the TDNAC calculation step for midsize molecules.