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Analytic high-order Douglas-Kroll-Hess electric field gradients
Department of Theoretical Chemistry, Lund University.ORCID iD: 0000-0001-7567-8295
2007 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 127, no 7, 074105- p.Article in journal (Refereed) Published
Abstract [en]

In this work we present a comprehensive study of analytical electric field gradients in hydrogen halides calculated within the high-order Douglas-Kroll-Hess (DKH) scalar-relativistic approach taking picture-change effects analytically into account. We demonstrate the technical feasibility and reliability of a high-order DKH unitary transformation for the property integrals. The convergence behavior of the DKH property expansion is discussed close to the basis set limit and conditions ensuring picture-change-corrected results are determined. Numerical results are presented, which show that the DKH property expansion converges rapidly toward the reference values provided by four-component methods. This shows that in closed-shell cases, the scalar-relativistic DKH(2,2) approach which is of second order in the external potential for both orbitals and property operator yields a remarkable accuracy. As a parameter-dependence-free high-order DKH model, we recommend DKH(4,3). Moreover, the effect of a finite-nucleus model, different parametrization schemes for the unitary matrices, and the reliability of standard basis sets are investigated.

Place, publisher, year, edition, pages
2007. Vol. 127, no 7, 074105- p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-143889DOI: 10.1063/1.2761880PubMedID: 17718604OAI: oai:DiVA.org:uu-143889DiVA: diva2:392344
Available from: 2011-01-26 Created: 2011-01-25 Last updated: 2015-01-08Bibliographically approved

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