Dielectric constants of liquid formamide, N-methylformamide and dimethylformamide via molecular Ornstein-Zernike theory

Kirkwood factors, yielding dielectric constants, are calculated from pair correlation functions, which are numerical solutions of the hypernetted-chain approximation of molecular Ornstein-Zernike (MOZ) theory. The combined influence of the molecular polarizability and the hydrogen bond strength is investigated. Using a reasonable diameter for the hydrogen size in the amide group, the MOZ Kirkwood factors and dielectric constants are in good agreement with the experimental values. This is explained by the statistical correlations between the orientations of two near molecules, This is consistent with hydrogen bonds, forming networks in formamide and chains in N-methylformamide. (C) 1997 Elsevier Science B.V.