Density functional theory on phase space

作者：Blanchard Philippe; Gracia Bondia Jose M; Varilly Joseph C^*

来源：International Journal of Quantum Chemistry, 2012, 112(4): 1134-1164.

DOI：10.1002/qua.23101

• density functional theory
• phase-space methods
• electron correlation calculations

Forty-five years after the point de depart [Hohenberg and Kohn, Phys Rev, 1964, 136, B864] of density functional theory, its applications in chemistry and the study of electronic structures keep steadily growing. However, the precise form of the energy functional in terms of the electron density still eludes usand possibly will do so forever [Schuch and Verstraete, Nat Phys, 2009, 5, 732]. In what follows we examine a formulation in the same spirit with phase space variables. The validity of HohenbergKohnLevy-type theorems on phase space is recalled. We study the representability problem for reduced Wigner functions, and proceed to analyze properties of the new functional. Along the way, new results on states in the phase space formalism of quantum mechanics are established. Natural Wigner orbital theory is developed in depth, with the final aim of constructing accurate correlation-exchange functionals on phase space. A new proof of the overbinding property of the Muller functional is given. This exact theory supplies its home at long last to that illustrious ancestor, the ThomasFermi model.

• 出版日期2012-2-5