Article

An Alternative Approach to the g-Matrix: Theory and Applications

  1. Hélène Bolvin Dr.

Article first published online: 30 JUN 2006

DOI: 10.1002/cphc.200600051

Issue

ChemPhysChem

ChemPhysChem

Volume 7, Issue 7, pages 1575–1589, July 10, 2006

Additional Information

How to Cite

Bolvin, H. (2006), An Alternative Approach to the g-Matrix: Theory and Applications. ChemPhysChem, 7: 1575–1589. doi: 10.1002/cphc.200600051

Author Information

  1. Laboratoire de Chimie Quantique, Institut de Chimie de Strasbourg, LC3-UMR 7177, 4 rue Blaise Pascal 67000 Strasbourg, France, Fax: (+33) 390-24-15-89

Publication History

  1. Issue published online: 30 JUN 2006
  2. Article first published online: 30 JUN 2006
  3. Manuscript Received: 26 JAN 2006

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Keywords:

  • ab initio calculations;
  • computer chemistry;
  • EPR spectroscopy;
  • radicals;
  • spin–orbit coupling

Abstract

Starting from the formula proposed by Gerloch and McMeeking in 1975, the electronic g-matrix is expressed as a sum of two matrices called Λ and Σ describing the orbital and spin contributions respectively. This approach is applied on benchmark diatomic and triatomic molecules, and on TiF3 and Cu(NH3)42+ using either CASPT2 or CCSD(T) methods to calculate the spin-free states and SO-RASSI to calculate spin–orbit coupling. Results compare very well to experimental data and to previous theoretical work; and, for each molecule, the anisotropy of the g-matrix is modeled by the mean of a few parameters.

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