Red-, blue-, or no-Shift in hydrogen bonds: a unified explanation

Joseph, Jorly ; Jemmis, Eluvathingal D. (2007) Red-, blue-, or no-Shift in hydrogen bonds: a unified explanation Journal of the American Chemical Society, 129 (15). pp. 4620-4632. ISSN 0002-7863

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We provide a simple explanation for X-H bond contraction and the associated blue shift and decrease of intensity in IR spectrum of the so-called improper hydrogen bonds. This explanation organizes hydrogen bonds (HBs) with a seemingly random relationship between the X-H bond length (and IR frequency and its intensity) to its interaction energy. The factors which affect the X-H bond in all X-H···Y HBs can be divided into two parts: (a) The electron affinity of X causes a net gain of electron density at the X-H bond region in the presence of Y and encourages an X-H bond contraction. (b) The well understood attractive interaction between the positive H and electron rich Y forces an X-H bond elongation. For electron rich, highly polar X-H bonds (proper HB donors) the latter almost always dominates and results in X-H bond elongation, whereas for less polar, electron poor X-H bonds (pro-improper HB donors) the effect of the former is noticeable if Y is not a very strong HB acceptor. Although both the above factors increase with increasing HB acceptor ability of Y, the shortening effect dominates over a range of Ys for suitable pro-improper X-Hs resulting in a surprising trend of decreasing X-H bond length with increasing HB acceptor ability. The observed frequency and intensity variations follow naturally. The possibility of HBs which do not show any IR frequency change in the X-H stretching mode also directly follows from this explanation.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:13527
Deposited On:12 Nov 2010 15:24
Last Modified:11 May 2012 11:34

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