物理化学学报 >> 1994, Vol. 10 >> Issue (05): 387-390.doi: 10.3866/PKU.WHXB19940502
曹泽星, 田安民, 鄢国森
Cao Ze-Xing, Tian An-Min, Yan Guo-Sen
The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB~- and HBC~- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several new low-lying electroinc states are found, and the linear triplet structures are found to have the lowest energy. For the anions, the ~2∑~+ states are lower in energy than the ~2Π states. For HCB, the ~3Π state is 15.38 kcal·mol~(-1) more stable than the ~3∑~- state, and for HBC the ~3Π is 2.51 kcal·mol~(-1) below the ~3∑~- state at the first order configuration interaction (FOCI) level. The barriers of the conversion of HBC(~3Π) to HCB(~3Π), HBC(~1Δ(~1A_1)) to HCB(~1A′C_s) and HBC(~1Δ(~1A_2)) to HCB(~1A″C_s) are 23.21, 12.97 and 21.09 kcal·mol~(-1), respectively. The activation energies of the conversion of HBC~-(~2∑~+) to HCB(~2∑~+) and HCB~-(~2Π) to HBC~-(~2Π) are 18.13 and 25.88 kcal·mol~(-1), respectively. A symmetry breaking phenomenon is observed in several states. The harmonic vibrational frequencies of the neutral molecules and the anions are also reported to provide information for the possible experimental observation of these species.
Spectra excited states,
曹泽星, 田安民, 鄢国森. HCB和HCB-的激发态光谱与态-态转化的理论研究[J]. 物理化学学报, 1994, 10(05): 387-390.
Cao Ze-Xing, Tian An-Min, Yan Guo-Sen. Theoretical Studies of Spectra of the Excited States and Conversion Barriers of a State to State HCB and HCB-[J]. Acta Phys. -Chim. Sin., 1994, 10(05): 387-390.
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