A set of molecular models based on quantum mechanical ab initio calculations and thermodynamic data

TL;DR

This paper introduces a rapid parameterization method for small molecule molecular models using quantum mechanical calculations and thermodynamic data, achieving accurate vapor-liquid equilibrium predictions.

Contribution

It presents a novel force field-based modeling strategy that combines QM calculations with experimental data for efficient small molecule model development.

Findings

Models accurately predict vapor-liquid equilibrium data within a few percent.

Method successfully applied to ten diverse small molecules.

Provides a systematic approach for rapid molecular model development.

Abstract

A parameterization strategy for molecular models on the basis of force fields is proposed, which allows a rapid development of models for small molecules by using results from quantum mechanical (QM) ab initio calculations and thermodynamic data. The geometry of the molecular models is specified according to the atom positions determined by QM energy minimization. The electrostatic interactions are modeled by reducing the electron density distribution to point dipoles and point quadrupoles located in the center of mass of the molecules. Dispersive and repulsive interactions are described by Lennard-Jones sites, for which the parameters are iteratively optimized to experimental vapor-liquid equilibrium (VLE) data, i.e. vapor pressure, saturated liquid density, and enthalpy of vaporization of the considered substance. The proposed modeling strategy was applied to a sample set of ten molecules from different substance classes. New molecular models are presented for iso-butane, cyclohexane, formaldehyde, dimethyl ether, sulfur dioxide, dimethyl sulfide, thiophene, hydrogen cyanide, acetonitrile, and nitromethane. Most of the models are able to describe the experimental VLE data with deviations of a few percent.