Journal ArticleDOI
Basis set expansion of the dirac operator without variational collapse
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TLDR
In this article, a review of the possible ways to avoid the variational collapse is given, in terms of various criteria that one wants to fulfill, and the most promising approach consists of a freeparticle Foldy-Wouthuysen (FW) transformation on operator level and a back transformation on matrix level (approaches C2 and C3).Abstract:
The eigenstates of the matrix representation of the Dirac operator for c → ∞ do not approach their nonrelativistic counterparts in the same basis. This wrong “Schrodinger limit” is shown to be the main reason for the phenomenon known as “variational collapse.” After a short review of existing proposals to overcome the “variational collapse,” a systematic study of the possible ways to avoid it is given. All discussed approaches are analyzed in terms of various criteria that one wants to fulfill. The most promising approach consists of a free-particle Foldy–Wouthuysen (FW) transformation on operator level and a back transformation on matrix level (approaches C2 and C3). This implies a modification of the free-electron part of the matrix representation of the Dirac operator and leads to the correct Schrodinger limit (and if one wishes even the correct Pauli limit) in the same basis (and to the exact results for a complete basis). The potential energy is unchanged, which makes the application to n -electron systems straightforward. Projection of the Dirac operator to positive energy states does not remove the variational collapse unless this is done in a very special way.read more
Citations
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Relativistic regular two‐component Hamiltonians
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Regular Two-Component Pauli-Like Effective Hamiltonians in Dirac Theory
Ch Chang,M. Pelissier,Ph Durand +2 more
TL;DR: In this paper, it is shown that the theory of effective Hamiltonians allows the determination of Pauli-like Hamiltonians that are regular enough to be used in variational calculations.
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An exact separation of the spin‐free and spin‐dependent terms of the Dirac–Coulomb–Breit Hamiltonian
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Relativistic Hamiltonians for Chemistry: A Primer
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References
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TL;DR: In this article, the state of the art in relativistic calculation of atomic structures is surveyed and the theory is modelled on the practice in non-relativistic calculations, using many-particle wave functions built from Dirac central field spinors.
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Foundations of the relativistic theory of many-electron atoms
TL;DR: In this paper, the authors generalize the response given long ago by a number theorist to a student who asked “Why is number theory useful?” His reply: “It is useful because one can get a Ph.D with it!”
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On the Interaction of Two Electrons
Gerald E. Brown,D. G. Ravenhall +1 more
TL;DR: A relativistic wave equation for helium-like systems which gives energy levels correct to within α 2 Ry is derived from quantum electrodynamics, care being taken in the handling of pair-production processes as discussed by the authors.
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Relativistic effects on re and de in agh and auh from all-electron dirac hartree-fock calculations
Yoon Sup Lee,A. D. McLean +1 more
TL;DR: In this article, relativistic correlation effects are markedly different from nonrelativistic in this molecule, and they conclude that relativism is not the case in AuH.