Molecular Bonding in an Orbital-Free-Related Density Functional Theory

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-01, Vol.126 (2), p.325-332
• Main Authors: Sillaste, Spencer, Thompson, Russell B
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.1c07128

A density functional theory based on polymer self-consistent field theory is applied to systems of two atoms in order to show that this approach is capable of predicted molecular bonding. Periodic table elements from hydrogen up to neon are examined and homonuclear diatomic molecules are found to form for H , N , O , and F , in agreement with known results. The heteronuclear molecules CO and HF, which are known to exist under ambient conditions, are also found to be stable. Bond lengths for most of these molecules agree with experimental results to within less than 8%, with the exception of O and F which deviate more significantly. The bonding energy for H is given and is within 16% of the known value, but fundamental vibrational frequencies do not agree well with experiment. The main approximations of the theory are very simple and include a Fermi-Amaldi correction to the electron-electron interaction to account for self-interactions and a basic expression for the Pauli potential to account for the exclusion principle. The self-consistent equations are solved in terms of basis functions that encode the cylindrical symmetry of diatomic molecules. Since orbitals are not used, the approach is related to orbital-free density functional theory.