Brick by Brick Computation of the Gibbs Free Energy of Reaction in Solution Using Quantum Chemistry and COSMO-RS

TL;DR

This paper discusses a computational approach to accurately determine the Gibbs free energy of reactions in solution by combining quantum chemistry and COSMO-RS, providing guidelines and benchmarks for balancing accuracy and computational cost.

Contribution

It introduces a workflow for calculating the Gibbs free energy of reactions in solution by integrating different computational methods and benchmarks their precision.

Findings

Separate computation of gas phase, thermal, and solvation contributions improves accuracy.

Benchmark results guide the choice of computational methods for different accuracy levels.

Illustrative example demonstrates the workflow on a hydrogenation reaction.

Abstract

The computational modelling of reactions is simple in theory but can be quite tricky in practice. This article aims at the purpose of providing an assistance to a proper way of describing reactions theoretically and provides rough guidelines to the computational methods involved. Reactions in liquid phase chemical equilibrium can be described theoretically in terms of the Gibbs free energy of reaction. This property can be divided into a sum of three disjunct terms, namely the gas phase reaction energy, the finite temperature contribution to the Gibbs free energy, and the Gibbs free energy of solvation. The three contributions to the Gibbs free energy of reaction can be computed separately, using different theoretico--chemical calculation methods. While some of these terms can be obtained reliably by computationally cheap methods, for others a high level of theory is required to obtain predictions of quantitative quality. In order to propose workflows which can strike the balance between accuracy and computational cost, a number of benchmarks assessing the precision of different levels of theory is given. As an illustrative example, the low-temperature hydrogenation reaction of acetaldehyde to ethanol in solvent toluene is shown.