SCF-Xα-SW electron densities with the overlapping sphere approximation

Abstract

Self consistent field-Xα-scattered wave (SCF-Xα-SW) calculations have been performed for a series of eight first and second row homonuclear diatomic molecules using both the touching (TS) and 25 per cent overlapping sphere (OS) versions. The OS deformation density maps exhibit much better quantitative agreement with those from other Xα methods, which do not employ the spherical muffin-tin (MT) potential approximation, than do the TS maps.

The OS version thus compensates very effectively for the errors involved in the MT approximation in computing electron densities. A detailed comparison between the TS- and OS-Xα-SW orbitals reveals that the reasons for this improvement are surprisingly specific. The dominant effect of the OS approximation is to increase substantially the electron density near the midpoint of bonding σ orbitals, with a consequent reduction of the density behind the atoms. A similar effect occurs for the bonding π orbitals but is less pronounced. These effects are due to a change in hybridization of the orbitals, with the OS approximation increasing the proportion of the subdominant partial waves and hence changing the shapes of the orbitals. It is this increased orbital polarization which so effectively compensates for the lack of (non-spherically symmetric) polarization components in the MT potential, when overlapping spheres are used.

Additional information

Notes on contributors

Blair N. McMaster

Also at Département de Chimie, Université de Montréal.