The second dielectric virial coefficient for hydrogen chloride

Abstract

The second dielectric virial coefficient for hydrogen chloride is evaluated for several intermolecular potentials for a range of temperature and is compared with experiment. The experimental value [4] is large and positive (∼ + 3600 cm⁶ mol^-2 at 19·3°C). The theoretical values at 19·3°C, allowing for the anisotropic polarizability, are, +33·9 for model A [12], -478 for model B [14] and +908 for model C [15]. Thus the comparison favours the intermolecular potential for model C, which contains an explicit ‘ hydrogen bond ’ term. However, since the theoretical value is a factor four too small it is not safe to assume that the ‘ hydrogen bond ’ interaction is necessarily the decisive feature of the intermolecular interaction.

It is suggested that the second dielectric virial coefficient, which is simple to calculate for polar molecules, should be used as a very discriminating test of proposed intermolecular potentials, especially those obtained by simulation studies of the solid and liquid.