The reaction path of the rcaction HCN + OH - CN + H2O was traced with Fukui’s theory of intrinsic reaction coordinate by using ab ini tio MO method (at UMP4/6-31G** level) with gradient technique. On this basis, the ...The reaction path of the rcaction HCN + OH - CN + H2O was traced with Fukui’s theory of intrinsic reaction coordinate by using ab ini tio MO method (at UMP4/6-31G** level) with gradient technique. On this basis, the dynamics properties along the reaction path was investigated by reaction path Hamiltonian theory. The rate constants of this reaction at different temperatures were calculated by conventional and variational transition state thcory with tunneling correction.The theoretically calculatcd rate constants are in good agreement with experimental results, this shows that the title reaction is an one step,direct reaction.展开更多
The dynamical properties on reaction path （IRC） in internal coordinates have been obtained, which in. clude ω<sub>K</sub> （frequencies orthogonal to IRC）, L<sub>K</sub> （vibrational modes...The dynamical properties on reaction path （IRC） in internal coordinates have been obtained, which in. clude ω<sub>K</sub> （frequencies orthogonal to IRC）, L<sub>K</sub> （vibrational modes）, B<sub>KF</sub> （coupling constants between the IRC and vibra tions orthogonal to it）, B<sub>KL</sub> （coupling constants between every two vibrations orthogonal to IRC）. A set of theory of teac. tion path in molecular internal coordinates has been also constructed. The dynamical properties, including ω<sub>K</sub>, B<sub>KF</sub> B<sub>KL</sub> of the reaction H<sup>1</sup>O<sup>2</sup>H<sup>3</sup>+H<sup>4</sup>→H<sup>1</sup>O<sup>2</sup>+H<sup>3</sup>H<sup>4</sup> have been calculated, which explicitly explain the interaction, chang ing trend and contribution of each chemical bond （including bond angle） in the reaction.展开更多
文摘The reaction path of the rcaction HCN + OH - CN + H2O was traced with Fukui’s theory of intrinsic reaction coordinate by using ab ini tio MO method (at UMP4/6-31G** level) with gradient technique. On this basis, the dynamics properties along the reaction path was investigated by reaction path Hamiltonian theory. The rate constants of this reaction at different temperatures were calculated by conventional and variational transition state thcory with tunneling correction.The theoretically calculatcd rate constants are in good agreement with experimental results, this shows that the title reaction is an one step,direct reaction.
基金Project supported by the National Natural Science Foundation of China (Grant No.29773007).
文摘The dynamical properties on reaction path （IRC） in internal coordinates have been obtained, which in. clude ω<sub>K</sub> （frequencies orthogonal to IRC）, L<sub>K</sub> （vibrational modes）, B<sub>KF</sub> （coupling constants between the IRC and vibra tions orthogonal to it）, B<sub>KL</sub> （coupling constants between every two vibrations orthogonal to IRC）. A set of theory of teac. tion path in molecular internal coordinates has been also constructed. The dynamical properties, including ω<sub>K</sub>, B<sub>KF</sub> B<sub>KL</sub> of the reaction H<sup>1</sup>O<sup>2</sup>H<sup>3</sup>+H<sup>4</sup>→H<sup>1</sup>O<sup>2</sup>+H<sup>3</sup>H<sup>4</sup> have been calculated, which explicitly explain the interaction, chang ing trend and contribution of each chemical bond （including bond angle） in the reaction.
