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Hydrogen bond dynamics in solution

Abstract

THE key to understanding the broad but featureless νs(XH) absorption bands of hydrogen-bonded species in solution has been the recognition by Bratos that the νσ (XHY) hydrogen bond stretching mode has a pronounced stochastic character, and that the νs(XH) mode rapidly loses its phase coherence as a result of its strong anharmonic coupling to the νσ (XHY) mode1. This idea has been further developed by Yarwood and Robertson2,3, who treat the dynamics of the νσ mode more precisely than does Bratos. The most detailed prediction of these theories is that the amplitude of modulation of the νs (XH) mode should be proportional to the r.m.s. amplitude of the νσ displacement coordinate r2, and should thus vary with temperature as (coth (ħω2/2kT))1/2, where ω2(=2πcν̄σ) is the angular frequency of the νσ mode. We report here an experimental confirmation of this prediction for a dilute solution of self-associated CD3OH in freon 11. We also investigate how the dynamics of the hydrogen bond vibration change as the solvent freezes, and we present evidence that at liquid helium temperature the νσ (XHY) mode can be regarded as a quantum-mechanical stochastic oscillator executing a strongly over-damped zero-point motion.

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BOURNAY, J., ROBERTSON, G. Hydrogen bond dynamics in solution. Nature 275, 46–48 (1978). https://doi.org/10.1038/275046a0

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