3p—3d intershell correlation effects in transition metal ions

✍ Scribed by Pierloot Kristine; Tsokos Eftimios; Roos Björn O.

• Publisher: Elsevier Science
• Year: 1993
• Tongue: English
• Weight: 647 KB
• Volume: 214
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(93)85687-j

✦ Synopsis

The effect of 3p correlation on the relative term energies in the (3d)" configurations of fust-row transition metal ions has been studied using CASSCF and multireference perturbation theory. It is shown that (3p)'+ ( 3d)2 excitations contribute a significant part to the relative energies. Out of a total correlation contribution of -1.6 1 eV to the ( 3d)8 ( 3F+ 3) excitation energy in Ni2+, -1.08 eV originates from the inter-shell double excitations. The corresponding numbers in Ti2+ are -1.16 and -0.37 eV, respectively. Similar but smaller effects are found for the neutral atoms.