Empirical modeling of the peptide amide I band IR intensity in water solution

An empirical correction to amide group vacuum force fields is proposed in order to account for the influence of the aqueous environment on the CvO stretching vibration ~amide I!. The dependence of the vibrational absorption spectral intensities on the geometry is studied with density functional theory methods at the BPW91/6-31G** level for N-methyl acetamide interacting with a variety of of water molecule clusters hydrogen bonded to it. These cluster results are then generalized to form an empirical correction for the force field and dipole intensity of the amide I (CvO stretch! mode. As an example of its extension, the method is applied to a larger ~b-turn model! peptide molecule and its IR spectrum is simulated. The method provides realistic bandwidths for the amide I bands if the spectra are generated from the ab initio force field corrected by perturbation from an ensemble of solvent geometries obtained using molecular dynamic simulations. © 2003 American Institute of Physics. @DOI: 10.1063/1.1622384#