Density Functional Partition Theory with Fractional OccupationsClick to copy article linkArticle link copied!
Abstract
Partition theory (PT) is a formally exact methodology for calculating the density of any molecule or solid via separate calculations on individual fragments. Just as Kohn−Sham density functional theory (DFT) introduces noninteracting fermions in an effective potential that is defined to yield the exact density of the interacting problem, in PT a global effective potential is found that ensures that the sum of the fragment densities is that of the full system. By combining the two, density functional partition theory (DFPT) produces a DFT scheme that yields the (in principle) exact molecular density and energy via Kohn−Sham calculations on fragments. We give the full formalism and illustrate DFPT in the general case of noninteger fragment occupations.
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