Analytic high-order Douglas–Kroll–Hess electric field gradients

Giampaolo Barone, Remigius Mastalerz, Markus Reiher, Roland Lindh

Risultato della ricerca: Articlepeer review

56 Citazioni (Scopus)

Abstract

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.
Lingua originaleEnglish
pagine (da-a)074105-1-074105-12
RivistaTHE JOURNAL OF CHEMICAL PHYSICS
Volume127
Stato di pubblicazionePublished - 2007

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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