Calculations of nuclear magnetic shielding in paramagnetic molecules
2003 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 118, no 6, 2550-2561 p.Article in journal (Refereed) Published
We propose and evaluate first principles methods for calculating the nuclear shielding tensor in open-shell, paramagnetic molecules, dealing with the case of small spin-orbit coupling that, in turn, implies the best applicability to light, organic compounds. The formalism is consistent up to second order in the fine structure constant, and includes orbital, fully anisotropic dipolar, and isotropic contact contributions to the tensor. The proposed method is implemented within the ab initio single- and multiconfiguration self-consistent field as well as density functional theory frameworks. The applications include small main-group radicals and larger nitroxide radicals. The analysis of the results and comparison with the experimental nuclear magnetic resonance data, which are available for the latter compounds, indicate promising accuracy and applicability of the density functional theory method to chemically interesting problems.
Place, publisher, year, edition, pages
2003. Vol. 118, no 6, 2550-2561 p.
HYPERFINE COUPLING-CONSTANTS, DENSITY-FUNCTIONAL CALCULATIONS, GENERALIZED GRADIENT APPROXIMATION, CONSISTENT-FIELD CALCULATIONS, SPIN-ORBIT PSEUDOPOTENTIALS, INHOMOGENEOUS ELECTRON-GAS, CORRELATION-ENERGY, EXCHANGE-ENERGY, WAVE-FUNCTIONS, RADICALS
IdentifiersURN: urn:nbn:se:kth:diva-13644DOI: 10.1063/1.1535904ISI: 000180564800012OAI: oai:DiVA.org:kth-13644DiVA: diva2:326853
QC 201006242010-06-242010-06-222010-09-23Bibliographically approved