An evaluation for geometries, formation enthalpies, and dissociation energies of diatomic and triatomic (C, H, N, O), NO3, and HNO3 molecules from the PAW DFT method with PBE and optB88-vdW functionals

TL;DR

This study evaluates the accuracy of PAW DFT with PBE and optB88-vdW functionals in predicting geometries, formation enthalpies, and dissociation energies for small molecules containing C, H, N, and O, extending to larger molecules NO3 and HNO3.

Contribution

It provides a comprehensive assessment of PAW DFT methods for small molecules, comparing results with experimental data and other computational approaches to guide future applications.

Findings

Geometric parameters match experimental data well.

Errors in formation enthalpies and dissociation energies are quantified.

PAW DFT shows reliable performance for small molecules.

Abstract

Structural geometries, formation enthalpies, and dissociation energies of all diatomic and triatomic molecules consisting of the four basic elements C, H, N, and/or O are calculated from the projector augmented wave (PAW) density functional theory (DFT) method with the PBE and optB88-vdW exchange-correlation functionals. The calculations are also extended to two larger molecules NO3 and HNO3, which consist of 4 and 5 atoms, respectively. In total, 82 molecules or isomers are considered in the calculations. The geometric parameters including 42 bond lengths and 15 bond angles of these molecules from the planewave DFT method are highly satisfactory, relative to available experimental data. The error analysis is also performed for 49 formation enthalpies and 138 dissociation energies (including 51 atomization energies as well as corresponding bond dissociation energies). The results are also compared with the previous data from various atomic-orbitals-based methods for molecules and from similar or different planewave DFT methods for various solids and other molecules. This provides an informative and instructive evaluation, especially for calculating the large-size material systems containing these small molecules as well as for further developing DFT methods.