H_2、D_2、CO与Pd同时反应的热力学耦合理论和排代效应

Thermodynamic coupling theory and substitution effect of the simultaneous reaction of palladium with H_2, D_2 and CO

应用密度泛函B3P86方法,对H(D)、C、O采用6-311++G^(**),对Pd采用相对论有效势SDD基集合进行理论计算,得到PdH(PdD)、PdCO、H_2、D_2、CO等分子的平衡几何和离解能.利用电子-振动近似理论,分别计算了在不同温度下Pd与氢、Pd与氘、以及Pd与CO反应的平衡常数及平衡分压.进而利用同时反应的热力学理论,研究Pd与H_2、D_2、CO同时反应的平衡组份、平衡分压力及其排代效应和相互耦合竞争效应.

The structures and energy of PdCO, PdH, and PdD were optimized by using the density functional method （B3P86） with the relativistic effective core potential （RECP） basis sets SDD for Pd and 6- 311＋＋-G＊＊ for H （D） and C, O. The reaction equilibrium constants and equilibrium pressures of Pd with H2, Pd with D2 and Pd with CO were calculated by means of the approximate theory of electron-vibration motion, respectively. And the reaction equilibrium component and the equilibrium pressures of Pd with H2, D2 and CO simultaneously were computed. Then the substitution effect and the coupling competition effect were investigated.