The structures of lithochlorosilylenoid H_2SiLiCl have been studied by RHF/STO-3G gradient method. Four equilibrium states and three isomerization transition states are located. The calcula- tion shows that the struct...The structures of lithochlorosilylenoid H_2SiLiCl have been studied by RHF/STO-3G gradient method. Four equilibrium states and three isomerization transition states are located. The calcula- tion shows that the structure with three-membered ring is the most stable one and the stability of the equilibrium structures is in the order of three-membered ring>p-complex>σ-complex >tetrahedron. The dipole moments, Mülliken populations, frontier molecular orbitals and peculiarities of various structures are also given and analyzed.展开更多
Variational transition state theory is used to study the kinetics of the reactions Li+HF and Li+HCl on the BO potential energy surfaces, fitted to ab initio values by Lagana et al. The saddle point, the location of ge...Variational transition state theory is used to study the kinetics of the reactions Li+HF and Li+HCl on the BO potential energy surfaces, fitted to ab initio values by Lagana et al. The saddle point, the location of generalized transition state and other kinetic features on the bottleneck of the po- tential energy surface are obtained. We point out that the location of generalized transition state tends to the direction in which the two atoms with larger reduced mass separate off. It can be determined whether a potential energy surface is accurate or not by a fine analysis of its bottleneck region and a comparison of kinetic calculation with experimental result. This is helpful for building a more accurate potential energy surface.展开更多
1-D quantum calculations of reaction probabilities have been carried out for the col- linear reaction Cl+HCl (v≤3)→ClH (v＇≤3)+Cl using hyperspherical coordinates. An LEPS po- tential energy surface with a shallow ...1-D quantum calculations of reaction probabilities have been carried out for the col- linear reaction Cl+HCl (v≤3)→ClH (v＇≤3)+Cl using hyperspherical coordinates. An LEPS po- tential energy surface with a shallow well depth of -3.22 KJ/mol has been used in the calculations. The state-to-state reaction probabilities have been calculated. According to the results obtained we found that the diagonal (v=v＇) reaction probabilities dominate over the off-diagonal (vv＇) reaction probabilities and the largest off-diagonal reaction probabilities are smaller than 0.1. The reaction probabilities show oscillation as a function of energy. Dynamic resonances strengthen for the potential energy surface with a well.展开更多
文摘The structures of lithochlorosilylenoid H_2SiLiCl have been studied by RHF/STO-3G gradient method. Four equilibrium states and three isomerization transition states are located. The calcula- tion shows that the structure with three-membered ring is the most stable one and the stability of the equilibrium structures is in the order of three-membered ring>p-complex>σ-complex >tetrahedron. The dipole moments, Mülliken populations, frontier molecular orbitals and peculiarities of various structures are also given and analyzed.
基金Project supported by the National Natural Science Foundation of China.
文摘Variational transition state theory is used to study the kinetics of the reactions Li+HF and Li+HCl on the BO potential energy surfaces, fitted to ab initio values by Lagana et al. The saddle point, the location of generalized transition state and other kinetic features on the bottleneck of the po- tential energy surface are obtained. We point out that the location of generalized transition state tends to the direction in which the two atoms with larger reduced mass separate off. It can be determined whether a potential energy surface is accurate or not by a fine analysis of its bottleneck region and a comparison of kinetic calculation with experimental result. This is helpful for building a more accurate potential energy surface.
文摘1-D quantum calculations of reaction probabilities have been carried out for the col- linear reaction Cl+HCl (v≤3)→ClH (v＇≤3)+Cl using hyperspherical coordinates. An LEPS po- tential energy surface with a shallow well depth of -3.22 KJ/mol has been used in the calculations. The state-to-state reaction probabilities have been calculated. According to the results obtained we found that the diagonal (v=v＇) reaction probabilities dominate over the off-diagonal (vv＇) reaction probabilities and the largest off-diagonal reaction probabilities are smaller than 0.1. The reaction probabilities show oscillation as a function of energy. Dynamic resonances strengthen for the potential energy surface with a well.
