Spin-orbit interaction in heavy group 13 atoms and TlAr

Leininger, Thierry; Berning, Andreas; Nicklass, Andreas; Stoll, Hermann; Werner, Hans‐Joachim; Flad, Heinz-Jürgen

doi:10.1016/s0301-0104(97)00043-8

Cited by 84 publications

(74 citation statements)

References 24 publications

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“…Genuine correlation eects come in with double excitations. In line with other authors [5,23], we ®nd that valence correlation involving the 6s6p shell leads to a moderate reduction in SO splitting, by about 250 cm À1 , while core-valence correlation, i.e. simultaneous excitations from the valence shell and the outercore 5p5d shells, overcompensates this reduction and leads to a net increase in SO splitting, due to electron correlation, by about 500 cm À1 .…”

Section: Atomic Resultssupporting

confidence: 92%

A small-core multiconfiguration Dirac-Hartree-Fock-adjusted pseudopotential for Tl - application to Tl X ( X = F, Cl, Br, I)

Metz

Schweizer

Stoll

et al. 2000

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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146

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A relativistic pseudopotential of the energyconsistent variety simulating the Tl 21 (1s ± 4f ) core has been generated by adjustment to multicon®guration Dirac±Hartree±Fock data based on the Dirac±Cou-lomb±Breit Hamiltonian. Valence ab initio calculations using this pseudopotential have been performed for atomic excitation energies and for spectroscopic constants of the X0 and A0 states of TlX (X = F, Cl, Br, I). Comparison is made to experiment and to four-component density functional results.A relativistic energy-consistent PP for Tl has been derived, using the following atomic valence Hamiltonian:Correspondence to: H. Stoll

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Section: Atomic Resultssupporting

confidence: 92%

A small-core multiconfiguration Dirac-Hartree-Fock-adjusted pseudopotential for Tl - application to Tl X ( X = F, Cl, Br, I)

Metz

Schweizer

Stoll

et al. 2000

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

Self Cite

146

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“…Since the SO effects are treated self-consistently in the reference DC-HF calculation, the Landé averaging of the reference valence fine-structure one-electron energies kills the SO energy splitting effects ͑first order͒ but not the valence SO polarization and relaxation effects ͑second and higher orders͒ which means that l ͑1͒ is not purely scalar. This was already noticed numerically by Leininger et al 7 when extracting relativistic energy-consistent PPs. In the particular case of thallium, for example, a positive shift 15 was introduced into the SOPP in order to recover from the Landé average of the total DC-HF fine-structure energies the scalarrelativistic all-electron energy.…”

Section: ͑45͒supporting

confidence: 64%

“…Vallet et al 6 with the energy-consistent relativistic pseudopotentials from Leininger et al 7 and the corresponding corepolarization potential ͑CPP͒. At the one-component SCF level, the SO splitting of the 2 P ground state was found to be equal to 7334.4 cm −1 .…”

Section: Introductionmentioning

confidence: 99%

On the accuracy of one-component pseudopotential spin-orbit calculations

Fromager

Visscher

Maron

et al. 2005

The Journal of Chemical Physics

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Improvements on current one-component extraction procedures of spin-orbit pseudopotentials are investigated for high accuracy computation of spin-orbit coupling energies. By means of the perturbation-theory formalism we first show that spin-orbit pseudopotentials, extracted at the one-component self-consistent-field level from a reference all-electron Dirac-Coulomb or Dirac-Coulomb-Breit calculation, include valence spin-orbit polarization and relaxation effects. As a consequence the use of these pseudopotentials in uncontracted spin-orbit configuration interaction ͑CI͒ with singles from the reference ground-state configuration gives rise to double counting of these spin-orbit effects. Two new methods that avoid such double counting have been investigated. The first, so-called "explicit" method, calculates explicitly, by means of a four-component spin-orbit CI, the double-counted spin-orbit effects and removes them from the pseudopotentials. Due to the nonadditivity of the core and valence spin-orbit effects as well as the so-called "pseudovariational collapse," this method is shown to be cumbersome. In the second "implicit" method the spin-orbit pseudopotential is extracted at the spin-orbit polarized and relaxed level by means of a single-excitation spin-orbit CI calculation. Atomic tests on iodine demonstrate the ability of the latter method to solve the double-counting problem.

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“…For elements of groups IV, V, and VI the parameters were taken from the work of Igel-Mann et al [43], although the cutoff parameters given in that reference are not optimal for the ECPnnMWB pseudopotentials. For group III elements, optimal cutoffs were taken from Leininger et al [44], while optimal cutoffs for the halogens were taken from the online version of the SDB pseudopotentials [45]. (The valence basis set was left unchanged.…”

Section: Application To Diatomic Moleculesmentioning

confidence: 99%

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe

Martin¹,

Sundermann²

2001

The Journal of Chemical Physics

1,314

992

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We propose large-core correlation-consistent pseudopotential basis sets for the heavy p-block elements Ga-Kr and In-Xe. The basis sets are of cc-pVTZ and cc-pVQZ quality, and have been optimized for use with the large-core (valence-electrons only) Stuttgart-Dresden-Bonn relativistic pseudopotentials.Validation calculations on a variety of third-row and fourth-row diatomics suggest them to be comparable in quality to the all-electron cc-pVTZ and cc-pVQZ basis sets for lighter elements. Especially the SDB-cc-pVQZ basis set in conjunction with a core polarization potential (CPP) yields excellent agreement with experiment for compounds of the later heavy p-block elements.For accurate calculations on Ga (and, to a lesser extent, Ge) compounds, explicit treatment of 13 valence electrons appears to be desirable, while it seems inevitable for In compounds. For Ga and Ge, we propose correlation consistent basis sets extended for (3d) correlation. For accurate calculations on organometallic complexes of interest to homogenous catalysis, we recommend a combination of the standard cc-pVTZ basis set for first-and second-row elements, the presently derived SDB-cc-pVTZ basis set for heavier p-block elements, and for transition metals, the small-core [6s5p3d] Stuttgart-Dresden 1 basis set-RECP combination supplemented by (2f 1g) functions with exponents given in the Appendix to the present paper.

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Spin-orbit interaction in heavy group 13 atoms and TlAr

Cited by 84 publications

References 24 publications

A small-core multiconfiguration Dirac-Hartree-Fock-adjusted pseudopotential for Tl - application to Tl X ( X = F, Cl, Br, I)

A small-core multiconfiguration Dirac-Hartree-Fock-adjusted pseudopotential for Tl - application to Tl X ( X = F, Cl, Br, I)

On the accuracy of one-component pseudopotential spin-orbit calculations

Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe

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