| 复合物HNO···H2O2内N-H···O蓝移氢键的理论研究 |
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| 引用本文： | 杨颙,张为俊,高晓明.复合物HNO···H2O2内N-H···O蓝移氢键的理论研究[J].中国化学,2006,24(7):887-893. |
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| 作者姓名： | 杨颙 张为俊 高晓明 |
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| 作者单位： | Environmental Spectroscopy Laboratory Anhui Institute of Optics and Fine Mechanics，Chinese Academy of Sciences，Hefei，Anhui 230031，China，Environmental Spectroscopy Laboratory，Anhui Institute of Optics and Fine Mechanics，Chinese Academy of Sciences，Hefei，Anhui 230031，China，Environmental Spectroscopy Laboratory，Anhui Institute of Optics and Fine Mechanics，Chinese Academy of Sciences，Hefei，Anhui 230031，China |
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| 基金项目： | Project supported by the National Natural Science Foundation of China(No.G20477043)，Knowledge Creative Program of Chinese Academy of Sciences(No.KJCX2-SW-H08). |
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| 摘 要： | A theoretical study on the blue-shifted H-bond N-H…O and red-shifted H-bond O-H…O in the complexHNO…H_2O_2 was conducted by employment of both standard and counterpoise-corrected methods to calculate thegeometric structures and vibrational frequencies at the MP2/6-31G(d),MP2/6-31 G(d,p),MP2/6-311 q G(d,p),B3LYP/6-31G(d),B3LYP/6-31 G(d,p) and B3LYP/6-311 G(d,p) levels.In the H-bond N-H…O,the calcu-lated blue shift of N-H stretching frequency is in the vicinity of 120 cm~(-1) and this is indeed the largest theoreticalestimate of a blue shift in the X-H…Y H-bond ever reported in the literature.From the natural bond orbital analy-sis,the red-shifted H-bond O-H…O can be explained on the basis of the dominant role of the hyperconjugation.For the blue-shifted H-bond N-H…O,the hyperconjugation was inhibited due to the existence of significant elec-tron density redistribution effect,and the large blue shift of the N-H stretching frequency was prominently due tothe rehybridization of sp~n N-H hybrid orbital.
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| 关 键 词： | 红色偏移氢键 蓝色偏移氢键 原子分子拓扑分析 键轨道分析 |
| 收稿时间： | 2005-08-22 |
| 修稿时间： | 2005-08-222006-03-22 |
Theoretical Study on N–H···O Blue‐shifted H‐Bond for HNO···H2O2 Complex |
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| YANG, Yong ZHANG, Wei-Jun GAO, Xiao-Ming.Theoretical Study on N–H···O Blue‐shifted H‐Bond for HNO···H2O2 Complex[J].Chinese Journal of Chemistry,2006,24(7):887-893. |
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| Authors: | YANG Yong ZHANG Wei-Jun GAO Xiao-Ming |
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| Institution: | Environmental Spectroscopy Laboratory, Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Hefei, Anhui 230031, China |
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| Abstract: | A theoretical study on the blue‐shifted H‐bond N–H···O and red‐shifted H‐bond O–H···O in the complex HNO···H2O2 was conducted by employment of both standard and counterpoise‐corrected methods to calculate the geometric structures and vibrational frequencies at the MP2/6‐31G(d), MP2/6‐31+G(d,p), MP2/6‐311++G(d,p), B3LYP/6‐31G(d), B3LYP/6‐31+G(d,p) and B3LYP/6‐311++G(d,p) levels. In the H‐bond N–H···O, the calculated blue shift of N–H stretching frequency is in the vicinity of 120 cm?1 and this is indeed the largest theoretical estimate of a blue shift in the X–H···Y H‐bond ever reported in the literature. From the natural bond orbital analysis, the red‐shifted H‐bond O–H···O can be explained on the basis of the dominant role of the hyperconjugation. For the blue‐shifted H‐bond N–H···O, the hyperconjugation was inhibited due to the existence of significant electron density redistribution effect, and the large blue shift of the N–H stretching frequency was prominently due to the rehybridization of spn N–H hybrid orbital. |
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| Keywords: | red-shifted H-bond blue-shifted H-bond atoms in molecules topological analysis natural bond orbital analysis |
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