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A simple scheme for magnetic balance in four-component relativistic Kohn-Sham calculations of nuclear magnetic resonance shielding constants in a Gaussian basis.
MedLine Citation:
PMID:  22239770     Owner:  NLM     Status:  In-Data-Review    
Abstract/OtherAbstract:
We report the implementation of nuclear magnetic resonance (NMR) shielding tensors within the four-component relativistic Kohn-Sham density functional theory including non-collinear spin magnetization and employing London atomic orbitals to ensure gauge origin independent results, together with a new and efficient scheme for assuring correct balance between the large and small components of a molecular four-component spinor in the presence of an external magnetic field (simple magnetic balance). To test our formalism we have carried out calculations of NMR shielding tensors for the HX series (X = F, Cl, Br, I, At), the Xe atom, and the Xe dimer. The advantage of simple magnetic balance scheme combined with the use of London atomic orbitals is the fast convergence of results (when compared with restricted kinetic balance) and elimination of linear dependencies in the basis set (when compared to unrestricted kinetic balance). The effect of including spin magnetization in the description of NMR shielding tensor has been found important for hydrogen atoms in heavy HX molecules, causing an increase of isotropic values of 10%, but negligible for heavy atoms.
Authors:
Małgorzata Olejniczak; Radovan Bast; Trond Saue; Magdalena Pecul
Publication Detail:
Type:  Journal Article    
Journal Detail:
Title:  The Journal of chemical physics     Volume:  136     ISSN:  1089-7690     ISO Abbreviation:  J Chem Phys     Publication Date:  2012 Jan 
Date Detail:
Created Date:  2012-01-13     Completed Date:  -     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  0375360     Medline TA:  J Chem Phys     Country:  United States    
Other Details:
Languages:  eng     Pagination:  014108     Citation Subset:  IM    
Affiliation:
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, PolandCentre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromso̸, N-9037 Tromso̸, NorwayLaboratoire de Chimie et Physique Quantique (UMR 5626), CNRS/Université de Toulouse 3 (Paul Sabatier), 118 route de Narbonne, 31062 Toulouse, France.
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