On the Nature of Blueshifting Hydrogen Bonds

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	On the Nature of Blueshifting Hydrogen Bonds
	Mo, Yirong ; Wang, Changwei ; Guan, Liangyu ; Braida, Benoit ; Hiberty, Philippe C. ; Wu, Wei ; Mo YR(莫亦荣) ; Wu W(吴玮)
刊名	http://dx.doi.org/10.1002/chem.201402189
	2014-07-01
关键词	CENTER-DOT-O ENERGY DECOMPOSITION ANALYSIS LOCALIZED MOLECULAR-ORBITALS GROUP-FUNCTION APPROXIMATION DENSITY-FUNCTIONAL THEORY UNUSUAL INTENSITY CHANGES INTERMOLECULAR INTERACTIONS VIBRATIONAL SPECTROSCOPY CHARGE-TRANSFER POLYATOMIC SYSTEMS
英文摘要	US National Science Foundation [CHE-1055310, CNS-1126438]; China Scholarship Council (CSC); National Science Foundation of China [20873106]; Ministry of Science and Technology of China [2011CB808504]; The block-localized wave function (BLW) method can derive the energetic, geometrical, and spectral changes with the deactivation of electron delocalization, and thus provide a unique way to elucidate the origin of improper, blueshifting hydrogen bonds versus proper, redshifting hydrogen bonds. A detailed analysis of the interactions of F3CH with NH3 and OH2 shows that blueshifting is a long-range phenomenon. Since among the various energy components contributing to hydrogen bonds, only the electrostatic interaction has long-range characteristics, we conclude that the contraction and blueshifting of a hydrogen bond is largely caused by electrostatic interactions. On the other hand, lengthening and redshifting is primarily due to the short-range n(Y) >sigma*(X H) hyperconjugation. The competition between these two opposing factors determines the final frequency change direction, for example, redshifting in F3CH center dot center dot center dot NH3 and blueshifting in F3CH center dot center dot center dot OH2. This mechanism works well in the series FnCl3-nCH center dot center dot center dot Y (n=0-3, Y=NH3, OH2, SH2) and other systems. One exception is the complex of water and benzene. We observe the lengthening and redshifting of the O-H bond of water even with the electron transfer between benzene and water completely quenched. A distance-dependent analysis for this system reveals that the long-range electrostatic interaction is again responsible for the initial lengthening and redshifting.
语种	英语
出版者	WILEY-V C H VERLAG GMBH
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89258]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Mo, Yirong,Wang, Changwei,Guan, Liangyu,et al. On the Nature of Blueshifting Hydrogen Bonds[J]. http://dx.doi.org/10.1002/chem.201402189,2014.
APA	Mo, Yirong.,Wang, Changwei.,Guan, Liangyu.,Braida, Benoit.,Hiberty, Philippe C..,...&吴玮.(2014).On the Nature of Blueshifting Hydrogen Bonds.http://dx.doi.org/10.1002/chem.201402189.
MLA	Mo, Yirong,et al."On the Nature of Blueshifting Hydrogen Bonds".http://dx.doi.org/10.1002/chem.201402189 (2014).