Spin-Orbit Coupling and Other Relativistic Effects in Atoms and Molecules

Ermler, Walter C.; Ross, Ronald J.; Christiansen, P. A.

doi:10.1016/s0065-3276(08)60615-2

Cited by 204 publications

(100 citation statements)

References 100 publications

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“…The details of the GRECP approach [22] and the GRECP generation procedure [20,21,23,24] can be found elsewhere. Let us recall that the GRECP operator contains non-local (separable) terms in addition to semilocal terms of the conventional RECP [25]. These new terms imply that different potentials are used for the valence and Rydberg (e.g.…”

Section: Relativistic Effective Core Potentialsmentioning

confidence: 99%

Towards relativistic ECP / DFT description of chemical bonding in E112 compounds: spin-orbit and correlation effects in E112X versus HgX (X=H, Au)

et al. 2006

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Abstract:The relativistic effective core potential (RECP) approach combined with the spinorbit DFT electron correlation treatment was applied to the study of the bonding of eka-mercury (E112) and mercury with hydrogen and gold atoms. Highly accurate small-core shape-consistent RECPs derived from Hartree-Fock-Dirac-Breit atomic calculations with Fermi nuclear model were employed. The accuracy of the DFT correlation treatment was checked by comparing the results in the scalar-relativistic (spin-orbit-free) limit with those of high level scalar-relativistic correlation calculations within the same RECP model. E112H was predicted to be slightly more stable than its lighter homologue (HgH). The E112-Au bond energy is expected to be ca. 25-30 % weaker than that of Hg-Au. The role of correlations and magnetic (spin-dependent) interactions in E112-X and Hg-X (X=H, Au) bonding is discussed. The present computational procedure can be readily applied to much larger systems and seems to be a promising tool for simulating E112 adsorption on metal surfaces.

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Section: Relativistic Effective Core Potentialsmentioning

confidence: 99%

Towards relativistic ECP / DFT description of chemical bonding in E112 compounds: spin-orbit and correlation effects in E112X versus HgX (X=H, Au)

et al. 2006

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“…All core/valence interactions are represented by the REP, a one-electron operator which is present in that part of the F matrix containing the valence/valence interactions [16]. Therefore, solution of the Hartree-Fock-Roothaan or Dirac-Fock-Roothaan equations in this case involves diagonalization of the block containing the valence/valence interactions.…”

Section: The Relativistic Pseudopotentional In Atomic Calculationsmentioning

confidence: 99%

Relativistic Pseudopotentional Incorporating Core/Valence Polarization and Nonlocal Effects

Marino

2000

J. Chem. Inf. Comput. Sci.

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A relativistic pseudopotentional (RPP) for use in ab initio molecular electronic structure calculations is derived in the context of the relativistic effective core potential (REP) method of Lee et al. The resulting atom-specific RPP has salient features of the REP imbedded within it while retaining the form of a functional that is dynamically defined at runtime when used in calculations on molecules. The RPP is determined from Dirac-Fock wave functions for the isolated atom. Outer core two-electron interactions are incorporated into the RPP by means of variable coefficients that are defined in the context of the final molecular wave function. This form permits polarization of the outer core shells analogous to that occurring in all-electron molecular Hartree-Fock calculations while retaining these shells as part of the atomic pseudopotentional. Use of the RPP in post-Hartree-Fock molecular calculations permits the incorporation of core/valence correlation effects.

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“…The molecular D e values, given in Table VI, will be discussed below, but first the molecular spin-orbit effects will be discussed with the help of Tables III-V. In the literature many discussions exist rationalizing spin-orbit effects, especially in the context of ab initio calculations using relativistic effective core potentials ͑ECP͒, see, e.g., the reviews of Pitzer 25 and Ermler et al 26 In particular spin-orbit interaction was analyzed in terms of the bonding between the spin-orbit split ͑j j coupled͒ atomic spinors as a starting point. Here we will use the scalar relativistic approximation as our starting point and we will discuss how the molecular orbitals are modified by the presence of the spin-orbit interaction.…”

Section: Spin-orbit Effects In Closed Shell Moleculesmentioning

confidence: 99%

Construction of the Foldy–Wouthuysen transformation and solution of the Dirac equation using large components only

Lenthe

Baerends

Snijders

1996

The Journal of Chemical Physics

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Spin-Orbit Coupling and Other Relativistic Effects in Atoms and Molecules

Cited by 204 publications

References 100 publications

Towards relativistic ECP / DFT description of chemical bonding in E112 compounds: spin-orbit and correlation effects in E112X versus HgX (X=H, Au)

Towards relativistic ECP / DFT description of chemical bonding in E112 compounds: spin-orbit and correlation effects in E112X versus HgX (X=H, Au)

Relativistic Pseudopotentional Incorporating Core/Valence Polarization and Nonlocal Effects

Construction of the Foldy–Wouthuysen transformation and solution of the Dirac equation using large components only

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