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

Mastalerz, Remigius; Barone, Giampaolo; Lindh, Roland LU and Reiher, Markus (2007) In Journal of Chemical Physics 127(7).
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... (More)
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. (c) 2007 American Institute of Physics. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Physics
volume
127
issue
7
publisher
American Institute of Physics
external identifiers
  • wos:000248905300005
  • scopus:34548128304
ISSN
0021-9606
DOI
10.1063/1.2761880
language
English
LU publication?
yes
id
123be223-ef8c-4002-90d1-10c2549cb3f5 (old id 691807)
date added to LUP
2007-12-13 13:38:11
date last changed
2017-08-27 03:52:02
@article{123be223-ef8c-4002-90d1-10c2549cb3f5,
  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. (c) 2007 American Institute of Physics.},
  author       = {Mastalerz, Remigius and Barone, Giampaolo and Lindh, Roland and Reiher, Markus},
  issn         = {0021-9606},
  language     = {eng},
  number       = {7},
  publisher    = {American Institute of Physics},
  series       = {Journal of Chemical Physics},
  title        = {Analytic high-order Douglas-Kroll-Hess electric field gradients},
  url          = {http://dx.doi.org/10.1063/1.2761880},
  volume       = {127},
  year         = {2007},
}