Chapter 12. Douglas–Kroll–Hess Theory

  1. Prof. Dr. Markus Reiher and
  2. Dr. Alexander Wolf

Published Online: 22 JUN 2009

DOI: 10.1002/9783527627486.ch12

Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science

Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science

How to Cite

Reiher, M. and Wolf, A. (2009) Douglas–Kroll–Hess Theory, in Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527627486.ch12

Author Information

  1. ETH Zuerich, Laboratory for Physical Chemistry, Hoenggerberg Campus, Wolfgang-Pauli-Strasse 10, 8093 Zuerich, Switzerland

Publication History

  1. Published Online: 22 JUN 2009
  2. Published Print: 14 JAN 2009

ISBN Information

Print ISBN: 9783527312924

Online ISBN: 9783527627486

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Keywords:

  • Douglas–Kroll–Hess Theory;
  • sequential unitary decoupling transformations;
  • DKH Hamiltonians;
  • infinite-order DKH Hamiltonians;
  • arbitrary-order DKH method;
  • many-electron DKH Hamiltonians;
  • DKH calculations

Summary

Chapter 11 introduced the basic principles for elimination-of-the-small-component protocols and noted that the Foldy–Wouthuysen scheme applied to one-electron operators including scalar potentials yield ill-defined 1/c-expansions of the desired block-diagonal Hamiltonian. In contrast, the Douglas–Kroll–Hess transformation represents a unique and valid decoupling protocol for such Hamiltonians and is therefore investigated in detail in this chapter.