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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-0.05～0.05a.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.
Using B3P86 density functional theory and 6-311 ++ G (3df, 3pf) basis set, the effects of H2O, D2O, T2O, H2, D2, T2 and O2 under the dipole electric field of -0.05 ~ 0.05au Electron energy, nucleus kinetic energy and entropy, on the basis of this, we can calculate the kinetic energies and entropy values of H2O (g) → H2 (g) + O2 (g), D2O (g) → D2 (g) + O2 The enthalpy change ΔH, entropy change ΔS and Gibbs function ΔG of T2 → g (O2) → T2 (g) + O2 (g) finally obtained the reversible decomposition voltage Er of H2O, D2O and T2O.The calculated results show that H2O , Gibbs free energy (ΔG) and reversible decomposition voltage (Er) of D2O and T2O have obvious changes. When the external dipole electric field increases in the positive direction, Gibbs free energy change ΔG and reversible decomposition voltage Er tend to increase linearly. When the dipole field increases in the negative direction, the Gibbs free energy ΔG and the reversible decomposition voltage Er tend to decrease linearly. Under the same external dipole field, the Gibbs free energy ΔG and the reversible decomposition voltage Er change with the increase of H2O, D2O, T2O increase in turn.