Configurational temperatures and interactions in charge-stabilized colloid

Abstract

We demonstrate that the configurational temperature formalism can be derived from the classical hypervirial theorem, and introduce a hierarchy of hyperconfigurational temperature definitions, which are particularly well suited for experimental studies. We then use these analytical tools to probe the electrostatic interactions in monolayers of charge-stabilized colloidal spheres confined by parallel glass surfaces. The configurational and hyperconfigurational temperatures, together with a novel thermodynamic sum rule, provide previously lacking self-consistency tests for interaction measurements based on digital video microscopy, and thereby cast new light on controversial reports of confinement-induced like-charge attractions. We further introduce a new method for measuring the pair potential directly that uses consistency of the configurational and hyperconfigurational temperatures as a set of constraints for a model-free search.

15 pages, 12 figures, submitted to J. Chem. Phys