Kimberly Gleason*

ABSTRACT

Accurate modeling of catalytic reaction pathways requires consideration of thermal corrections and solvent effects on electronic energies and reaction intermediates. Zero-Point Vibrational Energy (ZPVE) corrections are essential for translating 0K electronic energies to finite-temperature observables. Harmonic vibrational analysis, combined with statistical mechanics, enables computation of thermodynamic quantities such as enthalpy, entropy, and free energy. The inclusion of solvation effects—either implicitly or explicitly—further enhances predictive accuracy, particularly for reactions in solution. Continuum solvation models, such as PCM, COSMO, and SMx, provide efficient computational treatment of solvent interactions. Recent developments in concentration-dependent free energy surfaces allow for realistic modeling of reaction conditions and catalyst behavior in liquid-phase systems, bridging the gap between idealized gas-phase calculations and practical catalytic applications. Keywords: Quantum Chemistry; Thermal Corrections; Zero-Point Vibrational Energy; Implicit Solvation; Explicit Solvation; Free Energy Surfaces; Catalysis; Reaction Pathways; Gibbs Free Energy; Enthalpy.