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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (10): 975-981. 上一篇    下一篇

研究论文

外偶极电场作用下H2O, D2O和T2O的可逆分解电压

史顺平1，罗文浪1,3，朱正和*,1，刘秀华2，傅依备2，蒋刚1，王蓉1，滑亚文1   

  1. (1四川大学原子与分子物理研究所 成都 610065)
    (2中国工程物理研究院 绵阳 621900)
    (3井冈山大学信息科学学院 吉安 343009)
  • 投稿日期:2009-07-14 修回日期:2009-11-19 发布日期:2009-12-23
  • 通讯作者: 史顺平 E-mail:shunping_999@sina.com

The Reversible Decomposition Voltages of H2O, D2O, T2O under the Dipole Electric Field

Shi Shunping1 Luo Wenlang1,3 Zhu Zhenghe*,1 Liu Xiuhua2 Fu Yibei2 Jiang Gang1 Wang Rong1 Hua Yawen1   

  1. (1 Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065)
    (2 China Academy of Engineering Physics, Mianyang 621900)
    (3 College of Information Science, Jinggangshan University, Ji an 343009)
  • Received:2009-07-14 Revised:2009-11-19 Published:2009-12-23

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采用密度泛函B3P86方法和6-311＋＋G(3df, 3pf)基组, 计算了在－0.05～0.05 a.u.外偶极电场作用下, H2O, D2O, T2O, H2, D2, T2, O2的电子能量、核运动能量和熵值, 在此基础上通过计算H2O(g)→H2(g)＋O2(g)、D2O(g)→D2(g)＋O2(g)、T2O(g)→T2(g)＋O2(g)的焓变ΔH、熵变ΔS、Gibbs函数变化ΔG, 最后得到了H2O, D2O, T2O的可逆分解电压Er. 计算结果表明, 外偶极电场存在时, H2O, D2O, T2O的Gibbs自由能变ΔG和可逆分解电压Er都有明显的变化, 当外偶极电场正方向增加时, 其Gibbs自由能变ΔG和可逆分解电压Er均趋于线性增加; 当外偶极电场负方向增加时, 其Gibbs自由能变ΔG和可逆分解电压Er均趋于线性减小; 在相同外偶极电场作用下, Gibbs自由能变ΔG和可逆分解电压Er随H2O, D2O, T2O依次增加.

关键词: H2O, D2O, T2O, 可逆分解电压Er, 外偶极电场, Gibbs自由能变ΔG

The electric energy, nuclear energy and entropy of H2O, D2O, T2O, H2, D2, T2, O2 were calculated under the dipole electric field from －0.05 to 0.05 a.u., employing B3P86 method of the density functional theory with basis sets 6-311＋＋G(3df, 3pf), by further calculating the enthalpy change ΔH, entropy change ΔS, Gibbs function change ΔG in the reaction of H2O(g)→H2(g)＋O2(g), D2O(g)→D2(g)＋O2(g), T2O(g)→T2(g)＋O2(g), the reversible decomposition voltage Er of H2O, D2O, T2O were obtained. The results show that the presence of dipole electric field will evidently influence the change of Gibbs free energy ΔG and the reversible decomposition voltage Er of H2O, D2O, T2O, for example, when the positive dipole electric field increases, the Gibbs free energy change ΔG and reversible decomposition voltage Er tend to a linear increase; but when the negative dipole electric field increases, the Gibbs free energy change ΔG and reversible decomposition voltage Er tend to a linear decrease, under the same dipole electric field, Gibbs free energy change ΔG and reversible decomposition voltage Er increase with the order of H2O, D2O, T2O.

Key words: H2O, D2O, T2O, reversible decomposition voltage, dipole electric field, Gibbs free energy