Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds

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	Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds
其他题名	Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds
	YANG Yong 1; ZHANG WeiJun1 ; PEI ShiXin 1; SHAO Jie 1; HUANG Wei1 ; GAO XiaoMing1
	2007
发表期刊	Science in China. Series B: Chemistry
ISSN	1006-9291
摘要	Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO…HNO, HCOOH…HNO, HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F. The geometric structures and vibrational frequencies of these six complexes at the MP2/6-31+G(d,p), MP2/6-311++G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO…HNO and HCOOH…HNO the N-H bond is strongly contracted and N-H…O blue-shifted hydrogen bonds are observed. While in complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F, the N-H bond is elongated and N-H…O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X-H bond length in the X-H…Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribution, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X-H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO…HNO and HCOOH…HNO, the shortening effects dominate which lead to the blue shift of the N-H stretching frequencies. In complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F where elongating effects are dominant, the N-H…O hydrogen bonds are red-shifted.
其他摘要	Theoretical calculations are performed to study the nature of the hydrogen bonds in complexes HCHO…HNO, HCOOH…HNO, HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F. The geometric structures and vibrational frequencies of these six complexes at the MP2/6-31+G(d,p), MP2/6-311++G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels are calculated by standard and counterpoise-corrected methods, respectively. The results indicate that in complexes HCHO…HNO and HCOOH…HNO the N-H bond is strongly contracted and N-H…O blue-shifted hydrogen bonds are observed. While in complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F, the N-H bond is elongated and N-H…O red-shifted hydrogen bonds are found. From the natural bond orbital analysis it can be seen that the X-H bond length in the X-H…Y hydrogen bond is controlled by a balance of four main factors in the opposite directions: hyperconjugation, electron density redistribution, rehybridization and structural reorganization. Among them hyperconjugation has the effect of elongating the X-H bond, and the other three factors belong to the bond shortening effects. In complexes HCHO…HNO and HCOOH…HNO, the shortening effects dominate which lead to the blue shift of the N-H stretching frequencies. In complexes HCHO…NH3, HCOOH…NH3, HCHO…NH2F and HCOOH…NH2F where elongating effects are dominant, the N-H…O hydrogen bonds are red-shifted.
关键词	red-shifted H-bond blue-shifted H-bond AIM topological analysis NBO analysis
收录类别	CSCD
语种	英语
CSCD记录号	CSCD:3191873
引用统计
文献类型	期刊论文
条目标识符	http://ir.hfcas.ac.cn:8080/handle/334002/94007
专题	中国科学院合肥物质科学研究院
作者单位	1.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences 2.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences 3.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences 4.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences 5.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences 6.Anhui Institute of Optics and Fine Mechanics, Chinese Academy of Sciences
第一作者单位	中科院安徽光学精密机械研究所
推荐引用方式 GB/T 7714	YANG Yong,ZHANG WeiJun,PEI ShiXin,等. Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds[J]. Science in China. Series B: Chemistry,2007,50.
APA	YANG Yong,ZHANG WeiJun,PEI ShiXin,SHAO Jie,HUANG Wei,&GAO XiaoMing.(2007).Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds.Science in China. Series B: Chemistry,50.
MLA	YANG Yong,et al."Theoretical study of the N-H…O red-shifted and blue-shifted hydrogen bonds".Science in China. Series B: Chemistry 50(2007).