Relativistic Pseudopotentials: Their Development and Scope of Applications
Theoretical Chemistry, University of Cologne, Greinstrasse 4, 50939 Cologne, Germany.Chemical Reviews (Impact Factor: 45.66). 09/2011; 112(1):403-80. DOI: 10.1021/cr2001383
Journal of Chemical Theory and Computation 11/2014; 10(11):4830-4841. DOI:10.1021/ct500762n · 5.31 Impact Factor
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ABSTRACT: Pseudopotentials simulate the interaction of the valence-electron system with frozen atomic cores using radially nodeless pseudo-orbitals. This leads to computational simplifications absent in frozen-core all-electron calculations. It is argued here that applying density fitting allows for using essentially the same (reduced) auxiliary basis sets for the valence interaction in both pseudopotential and all-electron calculations. We furthermore show that reduced auxiliary basis sets may also be made use of for fitting core Coulomb and exchange operators beyond on-site matrix elements. This leads to efficient substitutes for pseudopotentials in frozen-core all-electron calculations. At some pilot examples (Au-n, HfO, RnF6), we demonstrate the possibility to systematically improve the accuracy of standard pseudopotential calculations with limited additional computational effort.Journal of Chemical Theory and Computation 09/2014; 10(9):3857-3862. DOI:10.1021/ct500581h · 5.31 Impact Factor
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ABSTRACT: In this paper we present results of ab-initio calculations for the beryllium dimer with basis set of Slater-type orbitals (STOs). Nonrelativistic interaction energy of the system is determined using the frozen-core full configuration interaction calculations combined with high-level coupled cluster correction for inner-shell effects. Newly developed STOs basis sets, ranging in quality from double to sextuple zeta, are used in these computations. Principles of their construction are discussed and several atomic benchmarks are presented. Relativistic effects of order α 2 are calculated perturba-tively by using the Breit-Pauli Hamiltonian and are found to be significant. We also estimate the leading-order QED effects. Influence of the adiabatic correction is found to be negligible. Finally, the interaction energy of the beryllium dimer is determined to be 929.0 ± 1.9 cm −1 , in a very good agreement with the recent experimental value. The results presented here appear to be the most accurate ab-initio calculations for the beryllium dimer available in the literature up to date and probably also one of the most accurate calculations for molecular systems containing more than four electrons.Physical Review A 01/2015; 91:012510. DOI:10.1103/PhysRevA.91.012510 · 3.04 Impact Factor
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