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Relativistic Douglas–Kroll–Hess theory
Author(s) -
Reiher Markus
Publication year - 2011
Publication title -
wiley interdisciplinary reviews: computational molecular science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.126
H-Index - 81
eISSN - 1759-0884
pISSN - 1759-0876
DOI - 10.1002/wcms.67
Subject(s) - hamiltonian (control theory) , decoupling (probability) , eigenvalues and eigenvectors , physics , ab initio , quantum chemistry , quantum mechanics , dirac (video compression format) , electronic structure , relativistic quantum chemistry , quantum chemical , electron , dirac equation , total energy , ab initio quantum chemistry methods , quantum , theoretical physics , mathematical physics , molecule , mathematics , mathematical optimization , supramolecular chemistry , control engineering , neutrino , engineering , psychology , displacement (psychology) , psychotherapist
Relativistic effects on molecular properties and energies are ubiquitous in chemistry. Their consideration in quantum chemical calculations requires Dirac's theory of the electron, whose application is not without obstacles. Douglas–Kroll–Hess theory accomplishes a decoupling of positive‐ and negative‐energy eigenstates of the Dirac one‐electron Hamiltonian by an expansion in the external potential. At low orders, this expansion already converges and provides efficient relativistic Hamiltonians to be used in routine quantum chemical calculations. The basic principles of the approach are reviewed, and most recent developments are discussed. © 2011 John Wiley & Sons, Ltd. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods