Hydrogen bonds, infrared effects

In dimers composed of equal molecules the dimer components can replace each other through tunneling. This effect has been discovered by Dyke et al. [1972] as interconversion splitting of rotational levels of (HF)2 in molecular beam electric resonance spectra. This dimer has been studied in many papers by microwave and far infrared tunable difference-frequency laser spectroscopy (see review papers by Truhlar [1990] and by Quack and Suhm [1991]). The dimer consists of two inequivalent HE molecules, the H atom of one of them participating in the hydrogen bond between the fluorine atoms (fig. 60). PES is a function of six variables indicated in this figure. 

Intimate information about the nature of the H bond has come from vibrational spectro.scopy (infrared and Raman), proton nmr spectroscopy, and diffraction techniques (X-ray and neutron). In vibrational spectroscopy the presence of a hydrogen bond A-H B is manifest by the following effects ... 

Infrared studies show that when water is adsorbed on the surface, the background intensity in the hydroxyl region increases new bands may appear but hydrogen-bonding effects make such conclusions uncertain. If such a catalyst is then exposed to hydrogen (or deuterium), no bands due to adsorbed hydrogen (or deuterium) are observed. Thus, adsorption of water apparently occurs on the active sites and blocks out type I chemisorption. 

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