Hydrogen bond dynamics of methyl acetate in methanol

The H-bond interactions of methyl acetate in methanol have been studied by means of ab initio molecular dynamics simulations within the Car-Parrinello approach. It has been observed that the C=O stretching band of methyl acetate splits into a doublet as a consequence of the interaction with the solvent. The H-bond effects on the spectroscopic properties of methyl acetate in methanol have been interpreted by wavelet transform analysis in conjunction with a structural and dynamic characterization of the solvation cage. Localizing a vibrational mode in time and frequency during the simulations has allowed association of the different interactions with the solvent to the vibrational properties. This represents an important development in the capability of molecular dynamics simulations to explain experimental data obtained by time-resolved spectroscopic methods. © 2010 American Chemical Society.