TD-DFT spin-adiabats with analytic nonadiabatic derivative couplings

Authors

Nicole Bellonzi, University of Pennsylvania
Ethan Alguire, Schrodinger, Inc.
Shervin Fatehi, University of Texas Rio Grande ValleyFollow
Yihan Shao, University of Oklahoma Norman Campus
Joseph E. Subotnik, University of Pennsylvania

Document Type

Article

Publication Date

1-2020

Abstract

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.

Comments

This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in The Journal of Chemical Physics and may be found at https://doi.org/10.1063/1.5126440

Recommended Citation

Bellonzi, N., Alguire, E., Fatehi, S., Shao, Y., & Subotnik, J. E. (2020). TD-DFT spin-adiabats with analytic nonadiabatic derivative couplings. The Journal of Chemical Physics, 152(4), 044112. https://doi.org/10.1063/1.5126440

Publication Title

Journal of Chemical Physics

DOI

10.1063/1.5126440