A point-charge model for the nuclear quadrupole moment: Coupled-cluster, Dirac-Fock, Douglas-Kroll, and nonrelativistic Hartree-Fock calculations for the Cu and F electric field gradients in CuF

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dc.contributor.author Pernpointner, M. en
dc.contributor.author Seth, M. en
dc.contributor.author Schwerdtfeger, P. en
dc.date.accessioned 2009-09-03T04:39:28Z en
dc.date.available 2009-09-03T04:39:28Z en
dc.date.issued 1998 en
dc.identifier.citation Journal of Chemical Physics 108 (16), 6722-6738. 1998 en
dc.identifier.issn 0021-9606 en
dc.identifier.other eid=2-s2.0-0000626677 en
dc.identifier.uri http://hdl.handle.net/2292/5177 en
dc.description An open access copy of this article is available and complies with the copyright holder/publisher conditions. en
dc.description.abstract A point charge model for the nuclear quadrupole moment tensor (PCNQM) is developed in order to determine accurate electric field gradients (EFG) at the relativistic and correlated levels. The symmetric s contributions arising from the Poisson equation are avoided by using an appropriate point charge distribution in three-dimensional space. It is shown that the PCNQM model yields virtually the same EFGs compared to the conventional method of expectation values, if the point charges are set at small displacements from the nucleus (d<10-13 m) and the SCF energy is converged out to 12 significant figures. We further demonstrate that the choice of the point charge ? is not very critical to the PCNQM perturbation, and that the correlation energy at both the nonrelativistic and relativistic level of theory depends linearly on ?. This suggests that accurate EFG tensors can be obtained by performing only two correlated calculations for each atom and tensor component. The PCNQM model is tested on one-electron atoms and on the Cu and F EFG in CuF Relativistic and correlation effects on EFGs are discussed in detail. A Z-expansion on one-electron systems demonstrates that the relativistic correction scales ?Z5. For the CuF molecule Douglas-Kroll and Dirac-Fock coupled cluster calculations are in good agreement with each other. At the best level of theory (coupled cluster Dirac-Fock plus correction from basis set incompleteness) we obtain a nuclear quadrupole coupling constant for 63Cu of 23 Mhz. This is in very good agreement with the experimental result of 22 MHz considering the large standard deviation of the 63Cu nuclear quadrupole moment applied, 220(10) mb. en
dc.publisher American Institute of Physics (AIP) en
dc.relation.ispartofseries Journal of Chemical Physics en
dc.rights Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. Details obtained from http://www.sherpa.ac.uk/romeo/issn/0021-9606/ en
dc.rights.uri https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm en
dc.source.uri http://dx.doi.org/10.1063/1.476088 en
dc.title A point-charge model for the nuclear quadrupole moment: Coupled-cluster, Dirac-Fock, Douglas-Kroll, and nonrelativistic Hartree-Fock calculations for the Cu and F electric field gradients in CuF en
dc.type Journal Article en
dc.subject.marsden Fields of Research::240000 Physical Sciences en
dc.identifier.doi 10.1063/1.476088 en
pubs.issue 16 en
pubs.begin-page 6722 en
pubs.volume 108 en
dc.description.version VoR - Version of Record en
dc.rights.holder Copyright: 1998 American Institute of Physics. en
pubs.end-page 6738 en
dc.rights.accessrights http://purl.org/eprint/accessRights/OpenAccess en


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