| Summary: | 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 S₠(n π*) -> T₠(π π*) 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. The content is available under CC BY 4.0 License. This work was supported by the NRF funded by the Ministry of Science and ICT (2020R1A2C2008246 and 2020R1A5A1019141) and by the Samsung Advanced Institute of Technology (IO211126-09177-01) This work was also supported by the Korea Polar Research Institute (KOPRI, PE22120) funded by the Ministry of Oceans and Fisheries. T.Z. thanks the Natural Sciences and Engineering Research Council (NSERC) of Canada for research funding (RGPIN-2016-06276) and York University for start-up grant (481333). T.Z. also thanks Compute Canada and Digital Research Alliance of Canada for computational resources. Work by S.L. was funded by the US Department of Energy, Office of Science, via Award DE-SC0019374. Submitted - accurate-spin-orbit-coupling-and-intersystem-crossing-by-relativistic-mixed-reference-spin-flip-mrsf-tddft.pdf Supplemental Material - supporting-information.pdf
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