Linked Life Data

17129086

Source:http://linkedlifedata.com/resource/pubmed/id/17129086

Statements in which the resource exists as a subject.
PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
19
pubmed:dateCreated
2006-11-28
pubmed:abstractText
We have extended the frozen-density embedding (FDE) scheme within density-functional theory [T. A. Wesolowski and A. Warshel, J. Phys. Chem. 97, 8050 (1993)] to include external magnetic fields and applied this extension to the nonrelativistic calculation of nuclear magnetic resonance (NMR) shieldings. This leads to a formulation in which the electron density and the induced current are calculated separately for the individual subsystems. If the current dependence of the exchange-correlation functional and of the nonadditive kinetic-energy functional are neglected, the induced currents in the subsystems are not coupled and each of them can be determined without knowledge of the induced current in the other subsystem. This allows the calculation of the NMR shielding as a sum of contributions of the individual subsystems. As a test application, we have calculated the solvent shifts of the nitrogen shielding of acetonitrile for different solvents using small geometry-optimized clusters consisting of acetonitrile and one solvent molecule. By comparing to the solvent shifts obtained from supermolecular calculations we assess the accuracy of the solvent shifts obtained from FDE calculations. We find a good agreement between supermolecular and FDE calculations for different solvents. In most cases it is possible to neglect the contribution of the induced current in the solvent subsystem to the NMR shielding, but it has to be considered for aromatic solvents. We demonstrate that FDE can describe the effect of induced currents in the environment accurately.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Nov
pubmed:issn
0021-9606
pubmed:author
pubmed:issnType
Print
pubmed:day
21
pubmed:volume
125
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
194104
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Calculation of nuclear magnetic resonance shieldings using frozen-density embedding.
pubmed:affiliation
Faculty of Sciences, Department of Theoritcal Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands. jacob@few.vu.nl
pubmed:publicationType
Journal Article, Research Support, Non-U.S. Gov't