Tests of perturbative DFT total energy estimates implemented in a Gaussian basisThis article was presented at the 43rd Annual Sanibel Symposium, February 22–March 1, 2003.The delay in publication of this manuscript is not the fault of the authors.

We derive and test an approximate expression for the Kohn–Sham eigenfunctions and total energy associated with a given exchange‐correlation functional. The expression is closely related to the approximation given by Benoit et al. (Phys Rev Lett 2001, 87, 226401) but differs by removing an overly stringent orthogonality constraint. Tests on the Li, F, Ne, and Cr atoms done in Gaussian basis sets suggest that the approach is promising, particularly as an alternative to conventional self‐consistent field or to the Harris scheme (Phys Rev B 1985, 31, 1770). © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004 [ABSTRACT FROM AUTHOR]