Solvent mean force perturbations of diatomic dissociation reactions. Comparison of perturbed hard fluid and computer simulation results

摘要: The perturbed hard fluid model, which separates solute–solvent interactions into repulsive sphere and mean field attractive contributions, is applied to predict solvent effects on the thermodynamics of diatomic dissociation reactions. Theoretically predicted changes in excess Gibbs free energy (ΔG), entropy (ΔS), enthalpy (ΔH), volume (ΔV) for a homonuclear dissolved monatomic solvent, with Lennard‐Jones solute atom–solvent atom solvent–solvent interaction potentials, are compared computer simulation results. model requires only one adjustable parameter, determined using results at single temperature density. This parameter used prediction reaction over entire vapor, liquid, supercritical regime. Furthermore, other reactions, well depth upon dissociation, can be by including ...