Work

Charge Transfer with a Spin. II: A Framework for Diabatization Which Localizes Charge and Spin

Year: 2026

Type: article

Abstract: We investigate a diabatization procedure that localizes charges (in real space) and localizes spins (in spin space) for open-shell systems that exhibit charge transfer in the presence of spin–orbit coupling. The procedure is applied to a two-state crossing between pairs of Kramers-restricted doublet states (which can also be considered effectively a four-state crossing). To generate the relevant diabatic states, we employ a two-step optimization over complex-unitary rotations that sequentially maximizes dipole and spin moments through iterative Jacobi sweeps; the resulting update rules are effectively equivalent to those of approximate joint diagonalization applied to charge and spin. The method converges rapidly and yields smooth diabatic potential energy surfaces that preserve dipole and spin properties (e.g., a smoothly varying spin quantization axis) along the reaction coordinate while maintaining time-reversal symmetry.

Source: The Journal of Physical Chemistry A

DOI: 10.1021/acs.jpca.6c03595

Authors: Alok Kumar, Zhen Tao, Zuxin Jin, Joseph E. Subotnik, Tian Qiu

Institutions: Princeton University, University of Pennsylvania, University of Rhode Island

Language: English

Topic: Advanced Chemical Physics Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: hybrid

Funders: National Science Foundation, Division of Chemistry

Awards: G2922833186, G30737101, Angular Momentum Conservation, Spin, and Nonadiabatic Dynamics