Fast and Accurate Computation of Nonadiabatic Coupling Matrix Elements Using the Truncated Leibniz Formula and Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory.

We present a fast and accurate numerical algorithm for computing the first-order nonadiabatic coupling matrix element (NACME). The algorithm employs the truncated Leibniz formula (TLF) approximation within the finite-difference method, which makes it easily applicable in connection with any wave function-based methodology. In this work, we used the algorithm in connection with the recently developed mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT, MRSF for brevity). The accuracy is assessed for NACME between the singlet electronic states of a dissociating hydrogen molecule. It is demonstrated that an intermediate approximation, TLF(1), affords a negligible numeric error on the order of ∼10-10 a.u. while enabling a fast computation of NACME. As the MRSF method yields the correct description of the dissociation curves of H2 for all the electronic states involved, the numeric TLF(1)/MRSF NACME values are in excellent agreement with the reference analytical values obtained by the full configuration interaction. For polyatomic molecules, the MRSF NAC vectors agree very closely with the MRCISD NAC vectors. Hence, the proposed protocol is a promising tool for the evaluation of NACMEs.