Effects of Global and Local Anharmonicities on the Thermodynamic Properties of Sulfuric Acid Monohydrate.

Abstract

We use state-of-the-art electronic structure calculation methods and large basis sets to obtain reliable values for the thermodynamic properties of sulfuric acid monohydrate and study the effects of vibrational anharmonicity on these properties. We distinguish between two forms of vibrational anharmonicity: local anharmonicity, which refers to the anharmonicity of the vibrational modes of a given cluster conformer, and global anharmonicity, which originates from accounting for the presence of different conformers in the first place. In our most accurate approach, we solve the nuclear Schrödinger equation variationally for the intermolecular large-amplitude motions, thus quantum-mechanically accounting for the presence of higher-energy conformers for both reactants and products, while using the standard vibrational perturbational approach for the other vibrational modes. This results in a value of -11.0 kJ/mol for the reaction Gibbs free energy at 298.15 K. When standard vibrational perturbational approaches are employed, the effects of local anharmonicity depend heavily on the choice of the electronic structure calculation basis set. In fact, better results can often be achieved by combining a simple harmonic treatment for the vibrational partition function with a statistical mechanical accounting of global anharmonicity. Thus, we recommend that future studies that intend to include anharmonicity start by accounting for the presence of higher-energy conformers and only then consider whether local anharmonicity calculations are feasible and necessary.