The geometries of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2 radicals were investigated by density functional theory（DFT） method. The calculated results indicate that all the three radicals have pyramidal shapes at their centers, and the aC is one top of the pyramids. Based on the DFT optimized geometries, the hyperfine coupling constants（hfec＇s） of the 19F atoms of the three radicals were calculated by B3LYP, MP2（full） and QCISD（full） methods. The calculated values agree with the experimental values, especially for the a values of Fa, the a values are 125.6× 10 -4, 104.2× 10 - 4, and 83.2×10 -4 T of CF3OCF2, CF3OCFCF3 and CF3OCF2CF2, respectively. These results better explain the experimental observation.
A general formula for the multi-dimensional Monte Carlo microcanonical nonadiabatic rate constant expressed in configuration space is applied to calculate the rate of intersystem crossing(ISC) between the ground(S0) and first excited triplet(T1) states for isocyanic acid.One-,two-and three-dimensional potential energy surfaces are constructed by coupled-cluster single-double CCSD calculations,which are used for Monte Carlo sampling.The calculated S0→T1 ISC rate is in good agreement with experimental findings,which gives us a reason to believe that the multi-dimensional Monte Carlo microcanonical nonadiabatic rate theory is a very effective method for calculating nonadiabatic transition rate of a polyatomic molecule.
ZHANG Feng1,2,FANG WeiHai1,LUO Yi2 & LIU RuoZhuang1 1 College of Chemistry,Beijing Normal University,Beijing 100875,China
