Temperature dependent structural changes in liquid benzene studied using neutron diffraction

We present neutron diffraction data for liquid benzene measured as a function of temperature from 10°C to 70°C. Isotopic substitution and Empirical Potential Structure Refinement were used to obtain a complete spatial and orientational understanding of nearest neighbour correlations. We find an increased prevalence of nearest neighbour molecules where the angle between the aromatic planes is perpendicular, and at an angle of around 60°, when the temperature is reduced. There is no significant change in prevalence parallel stacked arrangements of nearest neighbour molecules as a function of temperature. The structure of the increased local order is consistent with structural motifs observed in benzene dimers and clusters from quantum chemistry calculations in the literature.