Wepresent an algorithm for efficient calculation of analytic nonadiabatic derivative couplings between spin-adiabatic, time-dependent density functional theory states within the Tamm-Dancoff approximation. Our derivation is based on the direct differentiation of the Kohn-Sham pseudowavefunction using the framework of Ou et al. Our implementation is limited to the case of a system with an even number of electrons in a closed shell ground state, and we validate our algorithm against finite difference at an S1/T2 crossing of benzaldehyde. Through the introduction of a magnetic field spin-coupling operator, we break time-reversal symmetry to generate complex valued nonadiabatic derivative couplings. Although the nonadiabatic derivative couplings are complex valued, we find that a phase rotation can generate an almost entirely real-valued derivative coupling vector for the case of benzaldehyde.
Bellonzi, Nicole; Alguire, Ethan; Fatehi, Shervin; Shao, Yihan; and Subotnik, Joseph E., "TD-DFT spin-adiabats with analytic nonadiabatic derivative couplings" (2020). Chemistry Faculty Publications and Presentations. 65.
Journal of Chemical Physics
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