【作者】 汤丽娟； 程科； 张莉； 蒋刚； 朱正和； 杨本福； 龙兴贵； 罗顺忠；

【Author】 TANG Li-juan,CHENG Ke,ZHANG Li, JIANG Gang ,ZHU Zheng-He, YANG Ben-fu ,LONG Xing-gui, LUO Shun-zhong (Institute of Atomic and Molecular Physics, Sichuan University,Chengdu 610065,China; China Academy of Engineering Physics,Mianyang 621900,China)

【机构】 四川大学原子与分子物理所； 中国工程物理研究院；

【摘要】 采用Gaussoam03程序及密度泛函B3P86方法,对Zr原子调用外部基函数8s7p3d,对氢原子采用 6-311g 全电子基函数,优化出ZrH2分子的微观结构以及不同温度下气态ZrH2(D,T)的热力学函数。在ZrH2(D,T)(s)的E和S的过程中,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E,以电子和振动熵SEv代替分子处于固态熵的近似方法,计算了不同温度下金属Zr与氢同位素反应的△H0、△S0和△G0以及氢化反应平衡压力,并导出了氢化反应平衡压力与温度的关系。计算结果表明,温度为393．16K时,氢化反应平衡压力1．66×10-14Pa 与实验值1．02×10-14Pa接近;693．16K时,平衡压力为3．89×10-2与实验值3．56×10-2Pa复合较好;说明了这种理论近似方法对二氢化锆及其同位素生成热力学函数计算的可行性。更多还原

【Abstract】 Density functional (B3P86/8s7p3d) method for Zr and 6-311g based function for hydrogen isotopes have been used to optimize the structure of ZrH2 and calculate the thermodynamic functions of ZrH2, ZrD2 and ZrT2 at different temperature. The vibration energy or the electronic and vibration entropy of the gaseous molecules are approximately used as the energy or entropy of the solid. In this approximation, thermodynamic functions △H0, △S0, △G0 and hydrogen isotopes equilibrium pressure of the hydrogenating reaction have been calculated . Then we can fit the relations between temperature and equilibrium pressure. In this paper, hydrogen e quilibrium pressure (1. 66×10-14Pa) is close to experimental value(1. 02× 10-14Pa) at 393. 16K , hydrogen e quilibrium pressure is 3. 89×10-2Pa and the experimental value is 3. 56×10-2 Pa, which show that the approximate theory method is feasible to calculate the thermodynamic functions of ZrH2(D,T).更多还原