| P5H6+和P5Me6+全反式构象的理论研究 |
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| 引用本文： | 蒲志凤,李前树. P5H6+和P5Me6+全反式构象的理论研究[J]. 分子科学学报, 2008, 24(6) |
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| 作者姓名： | 蒲志凤 李前树 |
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| 作者单位： | 1. 北京理工大学化学物理研究所,北京,100081
2. 北京理工大学化学物理研究所,北京,100081;华南师范大学量子化学计算中心,广东,广州,510631 |
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| 摘 要： | 用HF和MP2两种从头算方法结合cc-pVDZ和cc-pVTZ两种基组对P5H6 及其甲基取代物P5Me6 的反式构象进行理论计算,各限制优化出11个反式构象.进而分别得到其构象势能面曲线,P5H6 势能面曲线是单调平滑的,其上只有一个稳定点(3T4)和一个过渡态(4T3),说明3T4构象是势能面上的全局最小点.而P5Me6 势能面曲线与P5H6 大致相同,不同的是在势能面曲线中还存在另一个稳定点,在HF或MP2用cc-pVDZ基组时为2E(φ=216°),在HF/cc-pVTZ时为2T1(φ=198°),并且,3T4和2E的能量非常接近.最后将这两势能面与四氢呋喃进行了比较.
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| 关 键 词： | 构象 势能面 从头算理论方法 全局最小点 |
Theoretical study on all trans conformations for P5H6+ and P5Me6+ |
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| PU Zhi-feng,LI Qian-shu. Theoretical study on all trans conformations for P5H6+ and P5Me6+[J]. Journal of Molecular Science, 2008, 24(6) |
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| Authors: | PU Zhi-feng LI Qian-shu |
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| Abstract: | The all-trans conformations on the full pseudorotational cycle for the cyclotetraphosphinophosphonium cation(P5H6 ) and its methyl-substituted derivative(P5Me6 ) were located systematically on their potential energy surfaces.The potential energy for the pseudorotational circuit of P5H6 is smooth and monotonic with only one minimum(3T4) and one maximum(4T3),but the analogous P5Me6 circuit has two minima.The P5H6 and P5Me6 potential surfaces appear to be qualitatively very different from that for the well investigated tetrahydrofuran.Since the 3T4 form of P5H6 avoids unfavorable eclipsing PH-PH and lone pair-lone interactions,it is the global minimum among all possible P5H6 configurations and conformations. |
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| Keywords: | conformation potential energy surface ab initio theoretical method global minimum |
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