Solvent-induced symmetry breaking

Abstract

Symmetry breaking can be induced in a number of ways including interactions with a solvent. An example is the triiodide ion which is centrosymmetric in the gas phase. Molecular dynamics simulations of the triiodide ion in solution have been used to investigate the extent of symmetry breaking in a variety of solvents. We find that the triiodide ion loses its symmetry in water, ethanol, and methanol which form hydrogen bonds with the ion. This results in a localization of charge at one end of the ion and breaking of the geometric symmetry. The extent of symmetry breaking increases as the temperature is lowered. Correlation times for interconversion are reported and the energetics of symmetry breaking are presented. Analogies are made with second-order phase transitions.