The "JK-only" approximation in density matrix functional and wave function theory.

Various energy functionals applying the "JK-only" approximation which leads to two-index two-electron integrals instead of four-index two-electron integrals in the electron-electron interaction term of the electronic energy are presented. Numerical results of multiconfiguration self-consistent field calculations for the best possible "JK-only" wave function are compared to those obtained from the pair excitation multiconfiguration self-consistent (PEMCSCF) method and two versions of density matrix functional theory. One of these is derived making explicit use of some necessary conditions for N representability of the second-order density matrix. It is shown that this method models the energy functional based on the best possible "JK-only" wave function with good accuracy. The calculations also indicate that only a minor fraction of the total correlation energy is incorporated by "JK-only" approaches for larger molecules. (c) 2004 American Institute of Physics