Enthalpy-entropy compensation is not a general feature of weak association.

摘要: Relationships between the enthalpy and entropy changes resulting from perturbations of a system have been discussed in literature for some time. Both positive correlations (compensation) negative (anti-compensation) ΔH ΔS observed various experimental contexts, including chemical reaction, physical association, solvation, protein folding. Many examples demonstrated to be statistical artifacts, but are genuine signatures molecular characteristics. In particular, recent claims that compensation is general feature bimolecular associations arising weak intermolecular interactions. We employ mechanical framework predict magnitude direction enthalpy−entropy correlation association. The theory links macroscale thermodynamic relationship potential parameters. Using harmonic approximation Lennard-Jones mod...