Molecular systems Dirac electrons

With a = 2/3 this is identical to the Dirac expression. The original method used a = 1, but a value of 3/4 has been shown to give better agreement for atomic and molecular systems. The name Slater is often used as a synonym for the L(S)DA exchange energy involving die electron density raised to the 4/3 power (1/3 power for the energy density). 

Covariant elements, molecular systems modulus-phase formalism, Dirac theory electrons, 267-268... 

The idea of calculating atomic and molecular properties from electron density appears to have arisen from calculations made independently by Enrico Fermi and P.A.M. Dirac in the 1920s on an ideal electron gas, work now well-known as the Fermi-Dirac statistics [19]. In independent work by Fermi [20] and Thomas [21], atoms were modelled as systems with a positive potential (the nucleus) located in a uniform (homogeneous) electron gas. This obviously unrealistic idealization, the Thomas-Fermi model [22], or with embellishments by Dirac the Thomas-Fermi-Dirac model [22], gave surprisingly good results for atoms, but failed completely for molecules it predicted all molecules to be unstable toward dissociation into their atoms (indeed, this is a theorem in Thomas-Fermi theory). 

For the computational investigation of molecular systems containing heavy atoms, such as transition metals, lanthanides, and actinides, we could neglect neither relativity nor electron correlation. Relativistic effects, both spin-free and spin-orbit, increase with the nuclear charge of atoms. Therefore, instead of the nonrelativistic Schrodinger equation, we must start with the Dirac equation, which has four-component solutions. For many-electron systems, the four-component Hamiltonian is constructed from the one-electron Dirac operator with an approximated relativistic two-electron operator, such as the Coulomb, Breit, or Gaunt operator, within the nopair approximation. The four-component method is relativistically rigorous, which includes both spin-free and spin-orbit effects in a balanced way. However it requires much computational time since it contains more variational parameters than the approximated, one or two-component method. 

The 1998 Nobel Prize for Chemistry, awarded to a physicist for inventing modem Density Functional Theory (DFT), signaled widespread recognition of DFT as the pre-eminent many-electron theory for predictive, materials-specific (chemically specific) calculation of extended and molecular systems. The original papers of modem DFT are those of Hohenberg and Kohn [1] and Kohn and Sham [2] (preceded by seminal work of Thomas, Fermi, Dirac, Slater, Caspar, Gombas, and others not of direct relevance). General references include [3-16]. 

In this section I will outline the different methods that have been used and are currently used for the computation of parity violating effects in molecular systems. First one-component methods will be presented, then four-component schemes and finally two-component approaches. The term one-component shall imply herein that the orbitals employed for the zeroth-order description of the electronic wavefunction are either pure spin-up spin-orbitals or pure spin-down spin-orbitals and that the zeroth-order Hamiltonian does not cause couplings between the two different sets ( spin-free Hamiltonian). The two-component approaches use Pauli bispinors as basic objects for the description of the electronic wavefunction, while the four-component schemes employ Dirac four-spinors which contain an upper (or large) component and a lower (or small) component with each component being a Pauli bispinor. 

We review the Douglas-Kroll-Hess (DKH) approach to relativistic density functional calculations for molecular systems, also in comparison with other two-component approaches and four-component relativistic quantum chemistry methods. The scalar relativistic variant of the DKH method of solving the Dirac-Kohn-Sham problem is an efficient procedure for treating compounds of heavy elements including such complex systems as transition metal clusters, adsorption complexes, and solvated actinide compounds. This method allows routine ad-electron density functional calculations on heavy-element compounds and provides a reliable alternative to the popular approximate strategy based on relativistic effective core potentials. We discuss recent method development aimed at an efficient treatment of spin-orbit interaction in the DKH approach as well as calculations of g tensors. Comparison with results of four-component methods for small molecules reveals that, for many application problems, a two-component treatment of spin-orbit interaction can be competitive with these more precise procedures. 

Solutions with positive and negative energies of a one-particle Dirac equation of a molecular system are represented by states where either electronic or positronic contributions of four-component wave functions dominate. With chemical systems in mind, electronic and positronic components are also referred to as large and small components, respectively. However, small components cannot simply be neglected or projected out to arrive at a simpler two-component description because, in an intrinsic fashion they also contribute in a fully relativistic description of a chemical system. Thus, a projection step, in which positronic components are discarded, can only be applied after a suitable decoupling of electron and positron degrees of freedom. Then the effects of the small components are implicitly accounted for. 

The next term, EX, is positive for all the molecular systems of interest for liquids. The name makes reference to the exchange of electrons between A and B. This contribution to AE is sometimes called repulsion (REP) to emphasize the main effect this contribution describes. It is a true quantum mechanical effect, related to the antisymmetry of the electronic wave function of the dimer, or, if one prefers, to the Pauli exclusion principle. Actually these are two ways of expressing the same concept. Particles with a half integer value of the spin, like electrons, are subjected to the Pauli exclusion principle, which states that two particles of this type cannot be described by the same set of values of the characterizing parameters. Such particles are subjected to a special quantum version of the statistics, the Fermi-Dirac statistics, and they are called fermions. Identical fermions have to be described with an antisymmetric wave function the opposite also holds identical particles described by an... 

Since the electrons of a molecular system are indistinguishable with respect to their properties (i.e., charge and mass) we may drop the electron label i and write the perturbed Dirac Hamiltonian as... 

P. J. C. Aerts, W. C. Nieuwpoort. On the Use of Gaussian Basis Sets To Solve the Hartree-Fock-Dirac Equation. II. Application to Many-Electron Atomic and Molecular Systems. Int. J. Quantum Chem., Quantum Chem. Symp., 19 (1986) 267-277. 

Heavy-element systems are involved in many important chemical and physical phenomena. However, they still present difficulties to theoretical study, especially in the case of solids containing atoms of heavy elements (with the nuclear charge Z > 50). In this short description of relativistic electronic-structure theory for molecular systems we follow [496] and add a more detailed explanation of the Dirac-Kohn-Sham (DKS) method. For a long time the relativistic effects underlying in heavy atoms had not been regarded as such an important effect for chemical properties because the relativistic effects appear primarily in the core atomic region. However, now the importance of the relativistic effects, which play essential and vital roles in the total natures of electronic structures for heavy-element molecular and periodic qrstems, is recognized [496]. 

The no-virtual-pair Dirac-Coulomb-Breit Hamiltonian, correct to second order in the fine-structure constant a, provides the framework for four-component methods, the most accurate approximations in electronic structure calculations for heavy atomie and molecular systems, ineluding aetinides. Electron correlation is taken into aeeount by the powerful coupled eluster approaeh. The density of states in actinide systems necessitates simultaneous treatment of large manifolds, best achieved by Fock-space coupled eluster to avoid intruder states, which destroy the convergence of the CC iterations, while still treating a large number of states simultaneously, intermediate Hamiltonian sehemes are employed. 

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