Campus Units

Chemistry

Document Type

Article

Publication Version

Published Version

Publication Date

8-2001

Journal or Book Title

Journal of Physical Chemistry A

Volume

105

Issue

35

First Page

8262

Last Page

8268

DOI

10.1021/jp011677r

Abstract

The spin−orbit splittings of low-lying states in third-row transition elements were calculated using both an effective core potential (ECP) method within the one-electron (Zeff) approximation and all-electron (AE) methods using three different approaches. The wave functions were obtained using the multiconfiguration self consistent field (MCSCF) method followed by second-order configuration interaction (SOCI) calculations. All calculated results, except for the ones on atomic Ir, are in reasonable agreement with the corresponding experimental observations. The unsatisfactory results for atomic Ir are attributed to the poor theoretical prediction of the adiabatic energy gap between the lowest two 4F states. This gap has an incorrect sign in AE calculations without scalar relativistic corrections, but the gap can be reproduced qualitatively if these corrections are added using the newly developed RESC (relativistic elimination of small components) scheme. As a result, the AE calculations with the RESC approximation give spin−orbit splittings similar to those obtained by the ECP calculations with the Zeff approximation.

Comments

Reprinted (adapted) with permission from Journal of Physical Chemistry A 105 (2001): 8262, doi:10.1021/jp011677r. Copyright 2001 American Chemical Society.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

Included in

Chemistry Commons

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