Chemical Physics Letters, Vol.390, No.4-6, 358-361, 2004
Towards the understanding of the spectroscopic behaviour of the C-H oscillator in C-H center dot center dot center dot O hydrogen bonds: the effect of solvent polarity
The effect of solvent polarity versus specific C-(HO)-O-... contacts on the vibrational vC-H mode is studied using CHCl3 as a model system. Ab initio SCI-PCM calculations show that the overall shift of the vC-H band, sometimes ascribed to the C-(HO)-O-... hydrogen bonding, can in fact be explained by the electrostatic interaction with a dielectric environment. The presence of a new X-H band assigned to the C-(HO)-O-... bonded forms - remains as the most reliable evidence of C-(HO)-O-... hydrogen bonding. (C) 2004 Elsevier B.V. All rights reserved.