In this paper, potential‐dependent transformations are used to transform the four‐component Dirac Hamiltonian to effective two‐component regular Hamiltonians. To zeroth order, the expansions give second order differential equations (just like the Schrodinger equation), which already contain the most important relativistic effects, including spin–orbit coupling. One of the zero order Hamiltonians is identical to the one obtained earlier by Chang, Pelissier, and Durand [Phys. Scr. 34, 394 (1986)]. Self‐consistent all‐electron and frozen‐core calculations are performed as well as first order perturbation calculations for the case of the uranium atom using these Hamiltonians. They give very accurate results, especially for the one‐electron energies and densities of the valence orbitals.

Relativistic regular two‐component Hamiltonians

Ever since its discovery, the Berry phase has permeated through all branches of physics. Over the last three decades, it was gradually realized that the Berry phase of the electronic wave function can have a profound effect on material properties and is responsible for a spectrum of phenomena, such as ferroelectricity, orbital magnetism, various (quantum/anomalous/spin) Hall effects, and quantum charge pumping. This progress is summarized in a pedagogical manner in this review. We start with a brief summary of necessary background, followed by a detailed discussion of the Berry phase effect in a variety of solid state applications. A common thread of the review is the semiclassical formulation of electron dynamics, which is a versatile tool in the study of electron dynamics in the presence of electromagnetic fields and more general perturbations. Finally, we demonstrate a re-quantization method that converts a semiclassical theory to an effective quantum theory. It is clear that the Berry phase should be added as a basic ingredient to our understanding of basic material properties.

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Berry phase effects on electronic properties

Quantum electrodynamical corrections to the fine structure of helium

https://th.fhi-berlin.mpg.de/site/uploads/Publications/CPC-180-2175-2009.pdf

Ab Initio Molecular Simulations with Numeric Atom-Centered Orbitals

We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

By a canonical transformation on the Dirac Hamiltonian for a free particle, a representation of the Dirac theory is obtained in which positive and negative energy states are separately represented by two-component wave functions. Playing an important role in the new representation are new operators for position and spin of the particle which are physically distinct from these operators in the conventional representation. The components of the time derivative of the new position operator all commute and have for eigenvalues all values between $\ensuremath{-}c$ and $c$. The new spin operator is a constant of the motion unlike the spin operator in the conventional representation. By a comparison of the new Hamiltonian with the non-relativistic Pauli-Hamiltonian for particles of spin \textonehalf{}, one finds that it is these new operators rather than the conventional ones which pass over into the position and spin operators in the Pauli theory in the non-relativistic limit. The transformation of the new representation is also made in the case of interaction of the particle with an external electromagnetic field. In this way the proper non-relativistic Hamiltonian (essentially the Pauli-Hamiltonian) is obtained in the non-relativistic limit. The same methods may be applied to a Dirac particle interacting with any type of external field (various meson fields, for example) and this allows one to find the proper non-relativistic Hamiltonian in each such case. Some light is cast on the question of why a Dirac electron shows some properties characteristic of a particle of finite extension by an examination of the relationship between the new and the conventional position operators.

Siegfried A. Wouthuysen

Papers

On the Dirac Theory of Spin 1/2 Particles and Its Non-Relativistic Limit