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化学学报
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化学学报 ›› 1999, Vol. 57 ›› Issue (10): 1123-1128. 上一篇    下一篇

研究论文

PH~3...H~2O体系分子间相互作用的从头计算MO研究

张愚;王一波;孙泽民;田安民   

  1. 贵州大学化学系.贵州;四川大学化学系.成都(610064)
  • 发布日期:1999-10-15

Ab initio MO study on the PH~3...H~2O complexes

Zhang Yu;Wang Yibo;Sun Zemin;Tian Anmin   

  1. Guizhou Univ., Dept of Chem.Guizhou;Sichuan Univ, Dept Chem. Chengdu(610064)
  • Published:1999-10-15

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在MP2/6-311++G(3d,3p)水平,对PH~3...H~2O体系可能存在的氢键复合物进行了全自由度能量梯度优化,发现PH~3...H~2O体系存在三个能量极小结构A,B和C。其中结构A和B以H~2O作为质子授体,结构C以PH~3作为质子授体,结构A较结构B和C分别稳定6.52kJ/mol和8.18kJ/mol。结构A具有C~s对称性,其结构中P原子和O原子间距离为354.78nm,键角OHP为171.35ⅲ,属于接近于直线的传统型氢键结构。进一步在高级电子相关校正的MP4SDTQ下,用6-311++G(3df,3pd)基加上键函数{3s3p2d1f},通过BSSE校正,精确计算了结构A的结合能为-10.84kJ/mol。

关键词: 从头计算法, 氢键, 相互作用, 磷化氢, 水

The intermolecular geometry of the weak hydrogen-bonded complex PH~3. ..H~2O was optimized using the second-order Moller-Plesset perturbation theory (MP2) at 6-311++G (3d, 3p) level. Three equilibrium structures (A, B and C) was found. The geometry A, which exhibits the conventional structural features of a hydrogen-bonded system with H~2O as the proton donor, is the most stable one in the three equilibrium structures. Using the geometry A, which has C~s symmetry and R(P...O)=354.78nm, correlation energy has been calculated with 6-311++G(3df, 3pd) basis set adding bond function {3s3p2d1f} using MP2, and MP4SDTQ. The computed binding energy is -10. 84kJ/mol at MP4SDTQ level.

Key words: AB INITIO CALCULATION, HYDROGEN BONDS, INTERACTIONS, PHOSPHOROUS HYDRIDE, WATER

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