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Analytic high-order Douglas-Kroll-Hess electric field gradients
Remigius Mastalerz1, Giampaolo Barone, Roland Lindh
1Laboratorium für Physikalische Chemie, ETH Zurich, Hönggerberg Campus, Wolfgang-Pauli Strasse 10, CH-8093 Zurich, Switzerland.
The Journal of Chemical Physics
|August 28, 2007
Summary
This study validates the high-order Douglas-Kroll-Hess (DKH) method for calculating electric field gradients in hydrogen halides. The DKH approach provides accurate, reliable results comparable to four-component methods.
Area of Science:
- Quantum Chemistry
- Relativistic Effects in Molecules
- Computational Chemistry
Background:
- Electric field gradients (EFGs) are crucial for understanding molecular properties and electronic structure.
- Scalar-relativistic methods are essential for accurate calculations involving heavy elements.
Purpose of the Study:
- To comprehensively study analytical electric field gradients in hydrogen halides.
- To assess the accuracy and reliability of the high-order Douglas-Kroll-Hess (DKH) approach for EFG calculations.
- To investigate the impact of picture-change effects and various computational parameters.
Main Methods:
- Utilized the high-order Douglas-Kroll-Hess (DKH) scalar-relativistic approach.
- Employed analytical calculations for electric field gradients and picture-change effects.
- Investigated the convergence of DKH property expansion near the basis set limit.
- Compared DKH results with four-component relativistic methods.
Main Results:
- Demonstrated the technical feasibility and reliability of high-order DKH unitary transformations for property integrals.
- Showed rapid convergence of DKH property expansion towards four-component reference values.
- Confirmed remarkable accuracy of the scalar-relativistic DKH(2,2) approach for closed-shell systems.
- Identified DKH(4,3) as a recommended parameter-dependence-free high-order DKH model.
Conclusions:
- The high-order DKH method is a reliable and accurate tool for calculating electric field gradients in hydrogen halides.
- Analytical treatment of picture-change effects is crucial for high accuracy.
- DKH(2,2) and DKH(4,3) offer excellent performance for scalar-relativistic EFG calculations.
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