Comparative analysis of blue-shifted hydrogen bond versus conventional   hydrogen bond in methyl radical complexes

doi:10.1002/qua.21090

CORC > 北京大学 > 化学与分子工程学院

	Comparative analysis of blue-shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes
	Tang, Kai ; Shi, Fu Qiang
刊名	国际量子化学杂志
	2007
关键词	hydrogen bond aug-cc-pVTZ bond critical point NBO analysis radical ELECTRON-DENSITY CHARGE-DENSITY BASIS-SETS AB-INITIO ATOMS
DOI	10.1002/qua.21090
英文摘要	Methyl radical complexes H3C center dot center dot center dot HCN and H3C center dot center dot center dot HNC have been investigated at the UMP2(full)/aug-cc-pVTZ level to elucidate the nature of hydrogen bonds. To better understand the intermolecular H-bond interactions, topological analysis of electron density at bond critical points (BCP) is executed using Bader's atoms-in-molecules (AIM) theory. Natural bond orbital (NBO) analysis has also been performed to study the orbital interactions and change of hybridization. Theoretical calculations show that there is no essential difference between the blue-shift H-bond and the conventional one. In H3C center dot center dot center dot HNC complex, rehybridization is responsible for shortening of the N-H bond. The hyperconjugative interaction between the single electron of the methyl radical and N-H antibonding orbital is up to 7.0 kcal/mol, exceeding 3.0 kcal/mol, the upper limit of hyperconjugative n(Y)-->sigma*(X-H) interaction to form the blue-shifted H-bond according to Alabugin's theory. (C) 2006 Wiley Periodicals, Inc.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000242706900015&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Physical; Mathematics, Interdisciplinary Applications; Physics, Atomic, Molecular & Chemical; SCI(E); EI; 23; ARTICLE; 3; 665-669; 107
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/251877]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Tang, Kai,Shi, Fu Qiang. Comparative analysis of blue-shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes[J]. 国际量子化学杂志,2007.
APA	Tang, Kai,&Shi, Fu Qiang.(2007).Comparative analysis of blue-shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes.国际量子化学杂志.
MLA	Tang, Kai,et al."Comparative analysis of blue-shifted hydrogen bond versus conventional hydrogen bond in methyl radical complexes".国际量子化学杂志 (2007).