Detailed Kinetic Modeling for Liquid-phase Reactions Based on Quantum Chemical Calculations

Abstract

This article demonstrates a detailed-modeling method for liquid-phase reactions using quantum chemical calculations combined with polarizable continuum models (QM/PCMs), and the decomposition mechanism of hydrazine nitrate in nitric acid solutions within this framework. The major difference between liquid- and gas-phase reactions is the presence of numerous solvent molecules surrounding reactants and products. The effects of solvent molecules on liquid-phase reactions can be classified as static and dynamic. The former is an effect that changes the potential energy of a solute molecule, while the latter is a relaxation or diffusion effect caused by collisions between solute and solvent molecules. Some of these contributions can be modeled using QM/PCMs; however, addressing all of them is currently a challenging task.