Self-consistent field, including exchange and superposition of configurations, with some results for oxygen

 Douglas Rayner Hartree W. Hartree and Bertha Swirles

Published:24 July 1939

 

 

Abstract

The calculation of approximate wave functions for the normal configurations of the ions O +++, O ++, O +, and neutral O, and the calculation of energy values from the wave functions, was carried out some years ago by Hartree and Black (1933)- In this work, the one-electron radial wave functions were calculated by the method of the selfconsistent field without exchange, but exchange terms were included in the calculation of the energy from these radial wave functions. In the energy calculations, the same radial wave functions were taken for each of the spectral terms arising from a single configuration; * consequently the ratios between the calculated intermultiplet separations were exactly those given by Slater’s (1929) theory of complex spectra, f The ratios between the observed intermultiplet separations, however, depart considerably from these theoretical values (for example, we have for 0 ++ (¹D - ¹S) / (³P - ¹D), calc. 3 : 2, obs. 1.04 :1), although the energies of the individual terms, and particularly the intermultiplet separation between the lower terms, show quite a good agreement with the observed values.

 

https://sci-hub.se/https://doi.org/10.1098/rsta.1939.0008