Description of the Interfacial Behavior of Benzonitrile at Icy Surfaces by Grand Canonical Monte Carlo Simulations.

The adsorption of benzonitrile at the surface of crystalline (Ih) and low-density amorphous (LDA) ice has been investigated by grand canonical Monte Carlo simulations at temperatures ranging from 50 to 200 K. It is found that, in spite of its rather large dipole moment of 4.5 D, benzonitrile molecules can only form a highly unsaturated monolayer on LDA ice, reaching not more than 50% of the surface concentration of the saturated monolayer even at the lowest temperature considered, and they practically do not adsorb on Ih ice. In spite of the observed weak ability of the benzonitrile molecules for being adsorbed, the estimated heat of adsorption at an infinitely low surface concentration of -66.8 ± 2.2 kJ/mol is rather large. This value includes the contribution of roughly -30 to -35 kJ/mol of a benzene ring, about -10 kJ/mol of a large molecular dipole moment, and about -20 to -25 kJ/mol of a benzonitrile-water H-bond, as estimated from comparisons with the heat of adsorption values of similar molecules. The surprisingly weak ability of benzonitrile for adsorption is thus attributed to the unusually strong cohesion between the molecules, considerably exceeding their adhesion to ice, as reflected in the 70-80 kJ/mol difference of the lateral and ice contributions to the binding energy of surface benzonitrile molecules in the presence of condensed benzonitrile.