First Principles Prediction of Enthalpies of Formation for Polycyclic Aromatic Hydrocarbons and Derivatives

Published

October 20, 2015

Author(s)

Thomas C. Allison, Donald R. Burgess Jr.

Abstract

In this article, the first principles prediction of enthalpies of formation is demonstrated for 669 polycyclic aromatic hydrocarbon (PAH) compounds and a number of related functionalized molecules. It is shown that by extrapolating density functional theory calculations to a large basis set limit and then applying a group-based correction scheme that good results may be obtained. Specifically, 
a mean unsigned deviation and root mean squared deviation from the experimental enthalpy of formation data of 5.0 kJ/mol and 6.4 kJ/mol, respectively, is obtained using this scheme. This computational scheme is economical to compute and straightforward to apply, while yielding results of reasonable reliability. The results are also compared for a smaller set of molecules to the predictions given by the G3B3 and G3MP2B3 variants of the Gaussian-3 model chemistry with a mean unsigned deviation and root mean squared deviation of 4.5 kJ/mol and 4.8 kJ/mol, respectively.

Citation

Journal of Physical Chemistry A

Volume

119

Pub Type

Journals

Download Paper

https://doi.org/10.1021/acs.jpca.5b07908

Keywords

enthalpy of formation, quantum chemistry, thermodynamics

Citation

Allison, T. and Burgess, D. (2015), First Principles Prediction of Enthalpies of Formation for Polycyclic Aromatic Hydrocarbons and Derivatives, Journal of Physical Chemistry A, [online], https://doi.org/10.1021/acs.jpca.5b07908 (Accessed October 7, 2025)