| Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules |
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| 作者姓名： | 刘安雯 胡水明 丁昀 朱清时 |
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| 作者单位： | Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China;Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China;Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China;Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China (Grant Nos 20103007 and 20473079). |
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| 摘 要： | Stretching vibrational band intensities of XH3 (X=N, Sb) molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model.The dipole moment surfaces of NH3 and SbH3 are calculated with the density functional theory and at the correlated MP2 level,respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides (NH3, PH3,AsH3 and SbH3) are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit.
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| 关 键 词： | 双极子 表面拉伸 反射色彩 红外光谱 强度 局部模式 |
| 收稿时间： | 2005-03-10 |
| 修稿时间： | 5/8/2005 12:00:00 AM |
Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules |
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| Liu An-Wen,Hu Shui-Ming,Ding Yun and Zhu Qing-Shi.Three-dimensional ab initio dipole moment surfaces and stretching vibrational band intensities of the XH3 molecules[J].Chinese Physics B,2005,14(10):1946-1953. |
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| Authors: | Liu An-Wen Hu Shui-Ming Ding Yun and Zhu Qing-Shi |
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| Institution: | Hefei National Laboratory for Physical Sciences at Microscale,Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China |
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| Abstract: | Stretching vibrational band intensities of XH3 (X=N, Sb) molecules are investigated employing three-dimensional dipole moment surfaces combined with the local mode Hamiltonian model.The dipole moment surfaces of NH3 and SbH3 are calculated with the density functional theory and at the correlated MP2 level,respectively. The calculated band intensities are in good agreement with the available experimental data. The contribution to the band intensities from the different terms in the polynomial expansion of the dipole moments of four group V hydrides (NH3, PH3,AsH3 and SbH3) are discussed. It is concluded that the breakdown of the bond dipole approximation must be considered. The intensity “borrowing” effect due to the wave function mixing among the stretching vibrational states is found to be less significant for the molecules that reach the local mode limit. |
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| Keywords: | overtone dipole moment infrared band intensity local mode |
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