Split electrons in partition density functional theory

• Published in: The Journal of chemical physics Vol. 156; no. 22; pp. 224113 - 224123
• Main Authors: Zhang, Kui, Wasserman, Adam
• Format: Journal Article
• Language: English
• Published: United States American Institute of Physics 14.06.2022
• Subjects: Charge transfer; Density functional theory; Diatomic molecules; Dipole moments; Electronegativity; Electrons; Fragments; Integers; Populations; Upper bounds
• DOI: 10.1063/5.0091024
• ISSN: 0021-9606; 1089-7690

Partition density functional theory is a density embedding method that partitions a molecule into fragments by minimizing the sum of fragment energies subject to a local density constraint and a global electron-number constraint. To perform this minimization, we study a two-stage procedure in which the sum of fragment energies is lowered when electrons flow from fragments of lower electronegativity to fragments of higher electronegativity. The global minimum is reached when all electronegativities are equal. The non-integer fragment populations are dealt with in two different ways: (1) An ensemble approach (ENS) that involves averaging over calculations with different numbers of electrons (always integers) and (2) a simpler approach that involves fractionally occupying orbitals (FOO). We compare and contrast these two approaches and examine their performance in some of the simplest systems where one can transparently apply both, including simple models of heteronuclear diatomic molecules and actual diatomic molecules with two and four electrons. We find that, although both ENS and FOO methods lead to the same total energy and density, the ENS fragment densities are less distorted than those of FOO when compared to their isolated counterparts, and they tend to retain integer numbers of electrons. We establish the conditions under which the ENS populations can become fractional and observe that, even in those cases, the total charge transferred is always lower in ENS than in FOO. Similarly, the FOO fragment dipole moments provide an upper bound to the ENS dipoles. We explain why and discuss the implications.