Adiabatic connection for strictly correlated electrons.

Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
The Journal of Chemical Physics (Impact Factor: 3.12). 09/2009; 131(12):124124. DOI: 10.1063/1.3239472
Source: arXiv

ABSTRACT Modern density functional theory (DFT) calculations employ the Kohn-Sham system of noninteracting electrons as a reference, with all complications buried in the exchange-correlation energy (E(XC)). The adiabatic connection formula gives an exact expression for E(XC). We consider DFT calculations that instead employ a reference of strictly correlated electrons. We define a "decorrelation energy" that relates this reference to the real system, and derive the corresponding adiabatic connection formula. We illustrate this theory in three situations, namely, the uniform electron gas, Hooke's atom, and the stretched hydrogen molecule. The adiabatic connection for strictly correlated electrons provides an alternative perspective for understanding DFT and constructing approximate functionals.

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