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Article

Amide I Vibrational Dynamics of N-Methylacetamide in Polar Solvents: The Role of Electrostatic Interactions

M. F. DeCamp, L. DeFlores, J. M. McCracken, and A. Tokmakoff*

Department of Chemistry and George R. Harrison Spectroscopy Laboratory, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139

K. Kwac and M. Cho*

Department of Chemistry and Center for Multidimensional Spectroscopy, Division of Chemistry and Molecular Engineering, Korea University, Seoul 136-701, Korea

J. Phys. Chem. B, 2005, 109 (21), pp 11016–11026

DOI: 10.1021/jp050257p

Publication Date (Web): May 7, 2005

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

The vibrational frequency of the amide I transition of peptides is known to be sensitive to the strength of its hydrogen bonding interactions. In an effort to account for interactions with hydrogen bonding solvents in terms of electrostatics, we study the vibrational dynamics of the amide I coordinate of N-methylacetamide in prototypical polar solvents: D₂O, CDCl₃, and DMSO-d₆. These three solvents have varying hydrogen bonding strengths, and provide three distinct solvent environments for the amide group. The frequency−frequency correlation function, the orientational correlation function, and the vibrational relaxation rate of the amide I vibration in each solvent are retrieved by using three-pulse vibrational photon echoes, two-dimensional infrared spectroscopy, and pump−probe spectroscopy. Direct comparisons are made to molecular dynamics simulations. We find good quantitative agreement between the experimentally retrieved and simulated correlation functions over all time scales when the solute−solvent interactions are determined from the electrostatic potential between the solvent and the atomic sites of the amide group.

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