Variational density matrix functional theory calculations with the lowestorder Yasuda functional
Abstract
Fully variational density matrix functional theory calculations reveal a critical flaw in the Yasuda functional derived from the contracted Schrödinger equation and the lowestorder cumulant expansions of the reduced density matrices. Although it yields finite energies in conjunction with finite basis sets, it appears to be unbound from below even for one of the simplest twoelectron systems, namely, the helium atom at the s limit, once a complete basis set is employed. This observation casts serious doubts upon its practical usefulness in electronic structure calculations.
 Publication:

Journal of Chemical Physics
 Pub Date:
 July 2002
 DOI:
 10.1063/1.1481384
 Bibcode:
 2002JChPh.117...67C
 Keywords:

 density functional theory;
 variational techniques;
 Schrodinger equation;
 higher order statistics;
 Calculus Of Variations;
 Matrices (Mathematics);
 Matrix Theory;
 Schroedinger Equation;
 Statistical Analysis;
 Wave Equations;
 31.15.Ew;
 02.30.Xx;
 03.65.Ge;
 Atomic and Molecular Physics;
 Densityfunctional theory;
 Calculus of variations;
 Solutions of wave equations: bound states