SCALED QUANTUM-MECHANICAL FORCE-FIELD FOR GLYCINE IN BASIC SOLUTION

We obtain scale factors for three glycinate-nH2O ab initio force fields, using the 4-31G basis set, that can be used in building a scaled quantum mechanical force field for alanine and, subsequently, for peptides in aqueous solutions. Force constants from the fully optimized glycinate-nH2O supermolecules were scaled by using experimentally determined vibrational frequencies of glycine in water at pH 13. Similar calculations were performed for methylamine and acetate. Scale factors for the stretching modes of acetate are within 2% of the related scale factors for glycinate. The scale factor for the NH2 scissor mode in methylamine is also in agreement with that of glycinate. Changes in the scale factors as a function of the number of hydrating water molecules were also similar between glycinate and acetate. Amine groups showed relatively small changes. Scale factors for glycinate with no hydrating molecules were extrapolated from the supermolecule results, since the optimized structure of isolated glycinate obtained with the 4-31G basis set yielded one imaginary frequency. Good agreements between calculated and experimental frequencies for glycinate, acetate, and methyl amine were obtained for each set of scale factors. Scaling appears to compensate for the systematic effects of hydration on force constants, making it possible to obtain reliable frequency predictions for amino acids in water without resorting to expensive supermolecule calculations.