Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation

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.