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EnglishIn 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.
R., M., Barone, G., R., L., & M., R. (2007). Analytic high-order Douglas–Kroll–Hess electric field gradients. THE JOURNAL OF CHEMICAL PHYSICS, 127, 074105-1-074105-12.
| Data di pubblicazione: | 2007 |
| Titolo: | Analytic high-order Douglas–Kroll–Hess electric field gradients |
| Autori: | |
| Citazione: | R., M., Barone, G., R., L., & M., R. (2007). Analytic high-order Douglas–Kroll–Hess electric field gradients. THE JOURNAL OF CHEMICAL PHYSICS, 127, 074105-1-074105-12. |
| Rivista: | |
| Digital Object Identifier (DOI): | http://dx.doi.org/10.1063/1.2761880 |
| 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. |
| Appare nelle tipologie: | 1.01 Articolo in rivista |
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|---|---|---|---|---|
| JCP_127_074105.pdf | N/A | Open Access Visualizza/Apri |
http://hdl.handle.net/10447/30280
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