Accurate Spin-Orbit Coupling and Intersystem Crossing by Relativistic Mixed-Reference Spin-Flip (MRSF)-TDDFT

25 October 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Relativistic MRSF-TDDFT is developed considering the spin-orbit coupling (SOC) within the mean-field approximation. The resulting SOC-MRSF faithfully reproduces the experiments with very high accuracy, which is also consistent with the values by four-component (4c) relativistic CASSCF and 4c-CASPT2 in the spin-orbit-energy splitting calculations of the C, Si and Ge atoms. Even for the fifth-row element Sn, the SOC-MRSF yielded accurate splittings (~3% error). In the SOC calculations of the molecular 4-thiothymine with a third-row element, SOC-MRSF values are in excellent agreement with those of SO-GMC-QDPT2 level, regardless of geometries and exchange-correlation functionals. The same SOC-MRSF predicted the anticipated chance of S1 (n pi*) -> T1 (pi pi*) intersystem crossing, even in thymine with only second-row elements. With its accuracy and practicality, thus, SOC-MRSF is a promising electronic structure protocol in challenging situations such as nonadiabatic molecular dynamics (NAMD) incorporating both internal conversions and intersystem crossings in large systems.


Relativistic Effect
Spin-Orbit Coupling
Intersystem Crossing

Supplementary materials

Supporting Information
Supporting Information of ``Accurate Spin-Orbit Coupling and Intersystem Crossing by Relativistic Mixed-Reference Spin-Flip (MRSF)-TDDFT''


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