甲酰氯异构化和光解的理论研究——从头算水平上的反应热力学、动力学分析

THEORETICAL STUDY ON THE ISOMERIZATIONPHOTODECOMPOSITION OF FORMYL CHLORIDE——Theoretical Calculation on Chemical Equilibrium Constants and Kinetical Rate Constants at ab initio Level

由于对化学反应体系解核运动Schrdinger方程困难,化学界常常求解参加反应粒子的电子运动Schrdinger方程,得到其电荷密度分布、自由价和键级等静态物理量,作为反应性指标;这虽有简明的优点,但往往缺乏传递性和统一性。如用电荷密度分布分析亲电反应,仅在同系物中有定性比较其反应性相对大小的意义,无定量价值。此外,用反应的势垒大小判断反应的难易,忽略了鞍点处曲率的影响,就动力学的Arrhenius速度常数公式看,

Using the equilibrium structures, energies and vibrational frequencies of formyl chloride, its transition states and products for its isomerization and photodecomposition, which had been obtained by Han and Liu, and using the kinetic computer program written by ns, we have calculated their thermodynamic functions, the changes of Gibbs functions and the equilibrium constants,the rate constants as well A factor of the titled reactions. Furthermore, the mechanism of the reactions has been analysied. Our calculated results are in good agreement with the experimental ones.In addition, as viewed from describing chemical reactivity, the peper gives how to use the results of ab initio MO theory calculating chemical equilibrium constants and kinetic rate constants.