The electronic structure of the PtH molecule: Fully relativistic configuration interaction calculations of the ground and excited states

Visscher, Lucas; Saue, Trond; Nieuwpoort, W.C.; Fægri, Knut; Gropen, Odd

doi:10.1063/1.465813

Cited by 109 publications

(76 citation statements)

References 38 publications

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“…26 This should be taken as an indication of two things: first, the quality of the spin-orbit operator is very high, and second, the spin-orbit and correlation effects can be decoupled to a large extent so that the latter can be handled in a separate spin-free calculation. We included in Table VI the results of an ͑unshifted͒ WB-AIMP MRCI͑SD͒ calculation, in which a much larger CI space including also double excitations from the same reference was used, 40 as well as the results of a Dirac-Hartree-Fock plus four-component CI ͑singles and doubles͒ calculation of Visscher et al 41 of a comparable level in the treatment of correlation. The results of both of them are quite close and show a reasonable agreement with the experiment, but significantly poorer than the sfss-WB-AIMP MRCI͑S͒ calculation; what emerges from the comparison is that the main source of the deviations from the experiment in the two unshifted calculations is not the treatment of the spin-orbit effects but the treatment of the correlation effects, which indirectly contaminates the spinorbit splittings.…”

Section: B Spin-orbit Calculationsmentioning

confidence: 99%

The ab initio model potential method: Third-series transition metal elements

Casarrubios

Seijo

1999

The Journal of Chemical Physics

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In this paper we present nonrelativistic and relativistic core ab initio model potentials ͑AIMPs͒ and valence basis sets for La and the third-series transition metal elements. The relativistic AIMPs are derived from atomic Cowan-Griffin calculations; they are made of a spin-free part and a one-electron spin-orbit operator according to Wood and Boring. The core potentials correspond to the 62-electron core ͓Cd,4f ͔. The valence basis sets are optimized and spin-orbit corrected. We present monitoring spin-free calculations on the atoms, singly ionized ions and monohydrides of the ten elements, which show a good performance overall. A spin-free-state-shifted spin-orbit-configuration interaction calculation on Pt, which uses empirical spin-free data and which is expected to be essentially free from spin-free deficiencies, points out that the quality of the spin-orbit operators is very good.

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Section: B Spin-orbit Calculationsmentioning

confidence: 99%

The ab initio model potential method: Third-series transition metal elements

Casarrubios

Seijo

1999

The Journal of Chemical Physics

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“…Recently Mosyagin et al 37 applied generalized potentials ͑GRECP͒ to simulate the atomic core within a two-component j j coupled picture. 7 For comparison purposes it, however, also has a nonrelativistic two-component option that forms the basis for the current work.…”

Section: Theorymentioning

confidence: 99%

“…[1][2][3][4][5] Rigorous methods including relativity in quantum chemical calculations start usually from the four-component Dirac-Coulomb ͑DC͒, DiracCoulomb-Gaunt ͑DCG͒ or Dirac-Coulomb-Breit ͑DCB͒ Hamiltonian. 6 The electronic correlation treatment is based on four-component spinors ͑four-spinors͒ 3,[7][8][9] in that case. However, these approaches are still computationally demanding and can be applied only on small and medium sized systems.…”

Section: Introductionmentioning

confidence: 99%

Inclusion of mean-field spin–orbit effects based on all-electron two-component spinors: Pilot calculations on atomic and molecular properties

Iliaš

Kellö

Visscher

et al. 2001

The Journal of Chemical Physics

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An implementation of a two-component all-electron ( j j/ ) treatment of both scalar and spinorbit relativistic effects in the MOLFDIR program suite is presented. Relativity is accounted for by Douglas-Kroll transformed one-electron operators: scalar ͑spin-free͒ and so called mean-field spinorbit terms. The interelectronic interaction is represented by the nonrelativistic Coulomb operator. High-level correlated calculations of properties of several systems ͑FO, ClO, Cl, O 2 ϩ , O 2 Ϫ , Tl, and TlH͒ where spin-orbit effects play a dominant role are presented and compared with other data. Agreement with Dirac-Coulomb͑-Gaunt͒ reference values is in general very good.

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“…In spite of the progress in the development and implementation of the 4-component methods [1][2][3][4][5][6] for relativistic calculations of the electronic structure of . heavy atoms and molecules, their applications to larger molecules are prohibitively demanding [4,5,7,8].…”

Section: Introductionmentioning

confidence: 99%

On the Accuracy of the Discretization Techniques in Approximate Relativistic Methods

Wozniak

Sadlej

2000

Acta Phys. Pol. A

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Several non-singular 2-component methods for relativistic calculations of the electronic structure of atoms and molecules lead to cumbersome operators which are partly defined in the coordinate representation and partly in the momentum representation. The replacement of the Fourier transform technique by the approximate resolution of identity in the basis set of approximate eigenvectors of the p2 operator is investigated in terms of the possible inaccuracies involved in this method. The dependence of the accuracy of the evaluated matrix elements on the composition of the subspace of these eigenvectors is studied. Although the method by itself appears to be quite demanding with respect to the faithfulness of the representation of the p2 operator, its performance in the context of the standard Gaussian basis sets is found to be encouragingly accurate. This feature is interpreted in terms of approximately even-tempered structure of the majority of Gaussian basis sets used in atomic and molecular calculations.

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The electronic structure of the PtH molecule: Fully relativistic configuration interaction calculations of the ground and excited states

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Cited by 109 publications

References 38 publications

The ab initio model potential method: Third-series transition metal elements

The ab initio model potential method: Third-series transition metal elements

Inclusion of mean-field spin–orbit effects based on all-electron two-component spinors: Pilot calculations on atomic and molecular properties

On the Accuracy of the Discretization Techniques in Approximate Relativistic Methods

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