Analytic atomic wave functions of NMCSCF quality: Applications

Concise analytic, nonorthogonal but selectively orthogonalizable, modified Laguerre type atomic orbitals are developed, providing conciseness, clear physical interpretation, and near‐equivalent accuracy with numerical multi‐configuration self‐consistent field, to atomic configuration interaction calculations. By analyzing the general Eckart theorem, which introduces an energy augmentation to the variational criterion for excited states, securing against variational collapse, we use them to calculate several excited atomic states known to be in danger of suffering from variational collapse. We also use them to calculate highly excited states, applied to computation of recently measured VUV spectra of He states near the second ionization threshold. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005