The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The re...The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The reaction rate constants of five temperetures were calculated by CVT involving the tunneling effects.展开更多
The fragments such as TiCl<sub>2</sub> are encountered in the study of the reaction mechanism about organometallic complexes and clusters. It is of significanoce to study the metastables for the investigat...The fragments such as TiCl<sub>2</sub> are encountered in the study of the reaction mechanism about organometallic complexes and clusters. It is of significanoce to study the metastables for the investigation of the reaction mechanism and the synthesis of a new type of clusters and organometallic complexes. Hoffmann and his co-workers developed isolobal analogue theory and proved it by using EHMO and other qualitative methods. However, in展开更多
Using ab initio molecular orbital theory at the SOCI/MCSCF/HF/DH+d level, the equilibrium geometries, total energies, harmonic vibrational frequencies, zerro point vibrational energy and potential energy curves of the...Using ab initio molecular orbital theory at the SOCI/MCSCF/HF/DH+d level, the equilibrium geometries, total energies, harmonic vibrational frequencies, zerro point vibrational energy and potential energy curves of the ground state and 8 excited states of Si2 molecule were obtained. The relationship between the bond length and the electronic codriguration of the state was discussed. The results revealed that bond length and the harmonic vibrational frequency of the molecule strongly depended upon the number of π-electrons in the bonding MO’s. The reported states 3Πg, 5∑,3△u,3∑. havenot been seen in literatures.展开更多
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 ne...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 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·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(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·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 25.88kcal·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.展开更多
文摘The transition state(TS) and Intrinsic Reaction Coordinate (IRC) for the titled reaction were traced by means of MCSCF/6-31G (210 configurations). The reaction activation energy of this reaction is 140.2KJ/mol. The reaction rate constants of five temperetures were calculated by CVT involving the tunneling effects.
基金Project supported by the National Natural Science Foundation of China
文摘The fragments such as TiCl<sub>2</sub> are encountered in the study of the reaction mechanism about organometallic complexes and clusters. It is of significanoce to study the metastables for the investigation of the reaction mechanism and the synthesis of a new type of clusters and organometallic complexes. Hoffmann and his co-workers developed isolobal analogue theory and proved it by using EHMO and other qualitative methods. However, in
文摘Using ab initio molecular orbital theory at the SOCI/MCSCF/HF/DH+d level, the equilibrium geometries, total energies, harmonic vibrational frequencies, zerro point vibrational energy and potential energy curves of the ground state and 8 excited states of Si2 molecule were obtained. The relationship between the bond length and the electronic codriguration of the state was discussed. The results revealed that bond length and the harmonic vibrational frequency of the molecule strongly depended upon the number of π-electrons in the bonding MO’s. The reported states 3Πg, 5∑,3△u,3∑. havenot been seen in literatures.
文摘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 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·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(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·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 25.88kcal·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.
