【摘要】 在有效原子实势近似下，采用 Ｇａｕｓｓｉａｎ ９８计算程序及 Ｂ３ＬＹＰ／ＳＤＤ密度泛函方法计算得到了 ＺｒＣｏ和ＺｒＣｏＨ分子的结构、力常数、离解能，能量（Ｅ）、熵（Ｓ）以及ＺｒＣｏ与氢同位素气体反应的热力学函数．在固态ＺｒＣｏ、ＺｒＣｏＨ（Ｄ、Ｔ）的Ｅ和Ｓ的计算中，近似以气态分子总能量中的振动能Ｅｖ代替该分子处于固态时的振动能量，以电子运动和振动运动熵ＳＥｖ代替分子处于固态的熵，在这种近似下，计算了不同温度下ＺｒＣｏ与Ｈ２、Ｄ２、Ｔ２反应的　Ｈ　、　 Ｇ　、　 Ｓ　及氢化反应平衡压力，导出了氢化反应温度与平衡压力的依赖关系．计算得出：ＺｒＣｏＨ、ＺｒＣｏＤ、ＺｒＣｏＴ的生成焓（３９８～５９８ Ｋ）分别为 ８２．８１、８１．５４和 ８０．４９ ｋＪ·ｍｏｌ－１，与实验结果有很好的一致性，表明这种近似处理方法是合理的，可以用于一些未知氢化物的热力学函数的近似计算。更多还原

【Abstract】 Density functional (B3LYP/SDD) method with relativistic effective core potential (RECP) have been used to optimize the structure of ZrCo and ZrCoH, and to calculate energy E, entropy S and enthalpy H of ZrCoH (D, T). Considering the characteristics of different motion types, the vibration energy or electronic and vi-bration entropy of the molecules is assumed to be the corresponding values of their solid states. H, S, G and hydrogen isotope equilibrium pressures of the hydrogenating reactions have been calculated based on this ap-proximation. The formation enthalpies for ZrCoH, ZrCoD and ZrCoT at temperature from 398 to 598 K are 82. 81, 81. 54 and 80. 49 kJ· mol-1 respectively. The results cohere with the experimental results. It means that the pre-sent method is somehow reasonable to theoretical study on thermodynamic functions of hydrogen storage materi-als.更多还原