Optimization of auxiliary basis sets for the LEDO expansion and a projection technique for LEDO–DFT

We present a systematic procedure for the optimization of the expansion basis for the limited expansion of diatomic overlap density functional theory (LEDO‐DFT) and report on optimized auxiliary orbitals for the Ahlrichs split valence plus polarization basis set (SVP) for the elements H, LiF, and NaCl. A new method to deal with near‐linear dependences in the LEDO expansion basis is introduced, which greatly reduces the computational effort of LEDO–DFT calculations. Numerical results for a test set of small molecules demonstrate the accuracy of electronic energies, structural parameters, dipole moments, and harmonic frequencies. For larger molecular systems the numerical errors introduced by the LEDO approximation can lead to an uncontrollable behavior of the self‐consistent field (SCF) process. A projection technique suggested by Löwdin is presented in the framework of LEDO–DFT, which guarantees for SCF convergence. Numerical results on some critical test molecules suggest the general applicability of the auxiliary orbitals presented in combination with this projection technique. Timing results indicate that LEDO–DFT is competitive with conventional density fitting methods. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1242–1253, 2005