Correlation of 1s binding energy with the average quantum mechanical potential at A nucleus

✍ Scribed by Maurice E. Schwartz

• Publisher: Elsevier Science
• Year: 1970
• Tongue: English
• Weight: 561 KB
• Volume: 6
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(70)85245-9

✦ Synopsis

Changes in binding energies of ls core electrons for C. N. 0. and F atoms in different moIecular environments have been studied by examination of negatives of inner-shell orbital energies (-Els) Krom ab initio "double-[ " quality LCAO SCF MO wavefunctions. As contrasted with many previous correlatioos of binding energies with point charge models. changes of orbital energies have been related to the potential at the nucleus on which the 1s orbital sits. properly calculated as a quantummechanical expectation value. The contribution of the 1s to the potential is insensitive to environment_ and consideration focuses on the "external potential" 'Pext due to the remainder of the system outside of the Is. Shifts in -El6 are in all cases nearly the same as shifts in %ed (using atomic unitsj. the average oE eleven cases giving A(-Els)/A@ext) = 1.11. An analysis of the equations. based on localized valence hIO% and supported by numerical examples. shows this to be a generally expected result. with some possible exceptions being outlined.