摘要
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 $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO} ) $$ which consists of the one-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO1} ) $$ and two-electron $$ (\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\frown}$}}{H} _{SO2} ) $$ 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(■) 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.
基金
Supported by the "QingLan" Talent Engineering Funds by Tianshui Normal University
