采用多种方法,配有多种基组对BCl和BCl2分子的基态蛄构进行优化计算,优选出B3P86/6-311++G(3df)方法时BCl分子进行计算得到基态为X1∑、键长RBCl=0.17159 nm,谐振频率为ωg=837.0003 cm-1;优选出QCISD/6-31G(d,p)方法对BCl2分子进行计算得到基态为X2A1,平衡棱间距RBCl=0.17284 nm、键角βClBCl=125.3466°、离解能Dg=8.0592 eV,并计算出了谐振频率和力常数.在此基础上,运用多体展式理论方法,推导出BCl2分子的解析势能函数,其等值势能面图准确呈现出BCl2分子的蛄构特征及能量变化曲线.由此讨论了Cl+BCl和B+ClCl分子反应的势能面特征.可用于研究该分子的微观反应动力学特性.%Many method has been used to optimize the possible ground state structures of BCl and BCl2 by the multi-basis set. The results show that the ground state of BCl molecule is of X1∑ state, RBCl=0. 17159 nm, ωe =837. 0003 cm-1 with B3P86/6-311++G(3df). The ground state of BCl2 molecule is of 2A1 state, the parameters of structure are RBCl=0 17284 nm, βClBCl = 125 3466°De=8. 0592 eV with QCISD/6-31G(d,p). And the harmonic frequency have calculationed at the same time. The potential energy functions of BCl2 have been derived from the many-body expansion theory. The potential energy functions describe correctly the configurations and the dissociation energies of the two ground-state molecules. Molecular reaction kinetics of Cl+BCl and B+ClCl based on the potential energy functions is discussed briefly, which is successfully used for describing molecular reaction dynamics.
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