The LCAO representation of Xα-SW molecular orbitals

The Xα-SW molecular orbital method generates one-electron orbitals which are numerical, and hence interpretation of the bonding characteristics of these orbitals must be inferred from electron density maps. In this paper a method is presented for the projection of LCAO MO’s out of the Xα-SW orbitals, based upon maximization of the total overlap. Lagrange multipliers in the method indicate how well the individual projected orbitals overlap the original orbitals. Numerical quadrature over direct space is used to calculate some of the required matrix elements. Results are presented for an extended Slater orbital projection applied to N2.