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The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field(CASSCF) method and simple group theory.Using the full Pauli-Breit spin-orbit coupling(SOC) operator(■) SO) which consists of the one-electron(■) SO1) and two-electron(■) SO2) terms,we estimate the strengths of the SOC(198.37 cm-1 when symmetry is imposed,and 211.35 cm-1 with no symmetry constraints),which plays an essential role in the spin transitions between different spin states.The calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal(trans-MinS0) as a primary product which subsequently gives a secondary product identified as thiolthioketene.Our calculated results are in close agreement with the experimental observations.
The potential energy surface crossings for 1,2-dithiete have been investigated using the complete active space self-consistent field (CASSCF) method and simple group theory. Using the full Pauli-Breit spin-orbit coupling (SOC) operator ) which consists of the one-electron (■) SO1) and two-electron (■) SO2) terms, we estimate the strengths of the SOC (198.37 cm- 1 when symmetry is imposed, and 211.35 cm- 1 with no symmetry constraints ), which plays an essential role in the spin transitions between different spin states. These calculations show that the photolysis of 1,3-dithiol-2-one leads to the formation of trans-dithioglyoxal (trans-MinS0) as a primary product which Following gives a secondary product identified as thiolthioketene. Our calculated results are in close agreement with the experimental observations.