The present paper covers the reaction ergodography for the addition of AlH3 to acetylene investigated by ab initio calculation with RHF/3-21G basis set. The changes in some physical properties along the reaction path ...The present paper covers the reaction ergodography for the addition of AlH3 to acetylene investigated by ab initio calculation with RHF/3-21G basis set. The changes in some physical properties along the reaction path (IRC) are presented. The formations of FMOs of the transition state have been analyzed according to the Fukui' s method. On the basis of the perturbation theory and Wolfsborg Helmholtz formula, we calculated the FMO' s energy orders of TS and its formation that shows the HOMO of TS consists of LUMO, HOMO of AlH3 and HOMO of HCCH.展开更多
The ab initio calculation have been performed on the addition of LiH to acetylene at RHF/ 3-21G basis set. The geometries and energies of the isolated reactant. molecular complex. transition state and product have bee...The ab initio calculation have been performed on the addition of LiH to acetylene at RHF/ 3-21G basis set. The geometries and energies of the isolated reactant. molecular complex. transition state and product have been determined on the singlet potential energy surface of the ground state. Our results indicate that there is a meta-stable molecular complex near the isolated reactant in the reaction pathway. The process from isolated reactant to molecular complex is a non-bonding-ex- changing reaction process, and the process from molecular complex to product is the rate-controlling step of the reaction. We also estimate the activated entropy and the frequency factor of the rate- controlling step by using the RRKM theory. The FMO analysis for the transition state reveals the HOMO of transition state to be formed from both HOMO-LUMO and HOMO-HOMO interactions.展开更多
The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium...The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium geometries and energies of the reactant,transition state and product,and obtained the activation energies,reaction heats,frequency factors and the activation entropies of these two reaction processes.The vibrational correlation from reactant to transition state indicated that the IRCs of 1,2-H shift and inversion processes were associated with the deformation modes of 1540 and 1208 cm^(-1),respectively.The vibrational coupling between normal coordinates in the inversion process would be helpful for selecting the inversion reaction channel.展开更多
Reaction ergodography for the addition of lithium hydride to acetylene indicates that the lithium hydride, in both monomeric and dimeric forms, reacts with the acetylene via two similar and competitive pathways. Hence...Reaction ergodography for the addition of lithium hydride to acetylene indicates that the lithium hydride, in both monomeric and dimeric forms, reacts with the acetylene via two similar and competitive pathways. Hence, we have obtained the pseudo-first-order rate constant of this reaction.展开更多
文摘The present paper covers the reaction ergodography for the addition of AlH3 to acetylene investigated by ab initio calculation with RHF/3-21G basis set. The changes in some physical properties along the reaction path (IRC) are presented. The formations of FMOs of the transition state have been analyzed according to the Fukui' s method. On the basis of the perturbation theory and Wolfsborg Helmholtz formula, we calculated the FMO' s energy orders of TS and its formation that shows the HOMO of TS consists of LUMO, HOMO of AlH3 and HOMO of HCCH.
文摘The ab initio calculation have been performed on the addition of LiH to acetylene at RHF/ 3-21G basis set. The geometries and energies of the isolated reactant. molecular complex. transition state and product have been determined on the singlet potential energy surface of the ground state. Our results indicate that there is a meta-stable molecular complex near the isolated reactant in the reaction pathway. The process from isolated reactant to molecular complex is a non-bonding-ex- changing reaction process, and the process from molecular complex to product is the rate-controlling step of the reaction. We also estimate the activated entropy and the frequency factor of the rate- controlling step by using the RRKM theory. The FMO analysis for the transition state reveals the HOMO of transition state to be formed from both HOMO-LUMO and HOMO-HOMO interactions.
基金This project was supported by the National Natural Science Foundation of China.
文摘The ab initio calculations have been performed on the reaction paths of 1,2-H shift and inversion processes of amino-carbene molecule by the Intrinsic Reaction Coordinate(IRC)method. We have determined the equilibrium geometries and energies of the reactant,transition state and product,and obtained the activation energies,reaction heats,frequency factors and the activation entropies of these two reaction processes.The vibrational correlation from reactant to transition state indicated that the IRCs of 1,2-H shift and inversion processes were associated with the deformation modes of 1540 and 1208 cm^(-1),respectively.The vibrational coupling between normal coordinates in the inversion process would be helpful for selecting the inversion reaction channel.
基金Supported by the National Natural Science Foundation of China
文摘Reaction ergodography for the addition of lithium hydride to acetylene indicates that the lithium hydride, in both monomeric and dimeric forms, reacts with the acetylene via two similar and competitive pathways. Hence, we have obtained the pseudo-first-order rate constant of this reaction.
