Simulation of Liquid Amides Using a Polarizable Intermolecular Potential Function

We have developed a polarizable intermolecular potential function (PIPF) for simulation of liquid amides. The PIPF potential includes a pairwise additive component, consisting of the familiar Lennard-Jones and Coulomb form, and a nonadditive polarization term. The empirical parameters were optimized through a series of statistical mechanical Monte Carlo simulations of liquid formamide, N-methylacetamide (NMA), N-methylformamide (NMF), and N,N-dimethylformamide (DMF). In deriving the empirical potential functions, bimolecular complexes of the amides dimers were studied by ab initio molecular orbital calculations using the 6-31G(d) basis set, and the results were compared with the PIPF predictions. The computed heats of vaporization and densities for the liquids using the final parameters are within 2% and 3% of experimental values, respectively. The polarization effects are found to be significant in all liquids, ranging from 6% for DMF to 14% for formamide of the total liquid energy. Electrostatic and pol...