Analytic high-order Douglas-Kroll-Hess electric field gradients
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/691807
- author
- Mastalerz, Remigius ; Barone, Giampaolo ; Lindh, Roland LU and Reiher, Markus
- organization
- publishing date
- 2007
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Journal of Chemical Physics
- volume
- 127
- issue
- 7
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000248905300005
- scopus:34548128304
- pmid:17718604
- ISSN
- 0021-9606
- DOI
- 10.1063/1.2761880
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Chemical Physics (S) (011001060)
- id
- 123be223-ef8c-4002-90d1-10c2549cb3f5 (old id 691807)
- date added to LUP
- 2016-04-01 11:44:31
- date last changed
- 2022-01-26 17:34:22
@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 (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Analytic high-order Douglas-Kroll-Hess electric field gradients}},
url = {{http://dx.doi.org/10.1063/1.2761880}},
doi = {{10.1063/1.2761880}},
volume = {{127}},
year = {{2007}},
}