Wavefunctions four-component

There exist several SCF codes for the solution of radial equations the Hartree-Fock [16] equations are only one example, and the case described above is that of the single configuration approximation, in which each electron has well-defined values of n and l. There exist several other possibilities as stressed above, in Hartree s original method, the exchange term was left out in the Hartree-Slater method [17], an approximate expression is used for the form of the exchange term. The Cowan code [20] is a pseudorelativistic SCF method, which avoids the complete four-component wavefunctions by simulating relativistic effects. 

In order to understand the physical meaning of the equation, the electron mass m and the speed of light c, which are both unity in atomic units, are explicitly written in this and the next sections. The a in Eq. (6.55) is called the Pauli spin matrix (Pauli 1925). This equation is invariant for the Lorentz transformation, because the momentum p = —/ V is the first derivative in terms of space. More importantly, this equation rsqu-irts four-component wavefunctions. 

The relativistic molecular calculations are very difiicult as long as they keep four-component wavefunctions according to the Dirac theory. The reduction to a two-component Pauli-like formalism within the effective Hamiltonian theory allows one to perform standard relativistic variational calculations. 

Substituting Eq. (2.74) for the a matrices and Eq. (2.79) for the four-component wavefunction, the Dirac equation can alternatively be written as two coupled two-component equations... 

According to the Dirac [36] electron theory, the relativistic wavefunction has four components in spin-space. With the Hermitian adjoint wave function , the quantum mechanical forms of the charge and current densities become [31,40]... 

The wavefunction iJ> must then be a 1 x 4 column vector with four components ... 

The time-dependent Schrodinger equation (2.43) presents a serious problem from the point of view of relativity theory it does not treat space and time in a symmetric way, because second-order derivatives of the wavefunction with respect to spatial coordinates are accompanied by a first-order derivative with respect to time. One way out, as actually proposed by Schrodinger and later known as the Klein-Gordon equation, would be to have also second-order derivatives with respect to time. However, that would lead to a total probability for the particle under consideration which would be a function of time, and to a variation of the number of particles of the universe (which, at the time, was completely unacceptable). In 1928, Dirac sought the solution for this problem, by accepting first-order derivation in the case of time and forcing the spatial derivatives to also be first order. This requires the wavefunction to have four components (functions of the spatial coordinates alone), often called a four-component spinor . 

Each relativistic wavefunction for the electron of H (and hydrogen-like atoms) has four components, as already mentioned for the simple case of a particle in a unidimensional box. For example, for the 2s orbital (level 2S1/2) we have (see, for example, ref. 34) ... 

HF theory (sections 5.2.3.1-5.2.3.6) starts with a total wavefunction or total MO vp which is a Slater determinant made of component wavefunctions or MOs jr. In section 5.2.3.1 we approached HF theory by considering the Slater determinant for a four-electron system ... 

The transformation of the Dirac Hamiltonian to two-component form is accompanied by a corresponding reduction of the wavefunction. As discussed in detail in section 2, the four-component Dirac spinor will have only two nonvanishing components, as soon as the complete decoupling of the electronic and positronic degrees of freedom is achieved, and can thus be used as a two-component spinor. This feature can be exploited to calculate expectation values of operators in an efficient manner. However, this procedure requires that some precautions need to be taken care of with respect to the representation of the operators, i.e., their transition from the original (4 x 4)-matrix representation (often referred to as the Dirac picture) to a suitable two-component Pauli repre-... 

The formalism described here to derive energy-consistent pseudopotentials can be used for one-, two- and also four-component pseudopotentials at any desired level of relativity (nonrelativistic Schrbdinger, or relativistic Wood-Boring, Douglas-Kroll-Hess, Dirac-Coulomb or Dirac-Coulomb-Breit Hamiltonian implicit or explicit treatment of relativity in the valence shell) and electron correlation (single- or multi-configurational wavefunctions. The freedom... 

Scalar relativistic effects (e.g. mass-velocity and Darwin-type effects) can be incorporated into a calculation in two ways. One of these is simply to employ effective core potentials (ECPs), since the core potentials are obtained from calculations that include scalar relativistic terms [50]. This may not be adequate for the heavier elements. Scalar relativity can be variationally treated by the Douglas-Kroll (DK) [51] method, in which the full four-component relativistic ansatz is reduced to a single component equation. In gamess, the DK method is available through third order and may be used with any available type of wavefunction. 

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. 

The relativistic correction for the kinetic energy in the Dirac equation is naturally applicable to the Kohn-Sham equation. This relativistic Kohn-Sham equation is called the Dirac-KohnSham equation (Rajagopal 1978 MacDonald and Vosko 1979). The Dirac-Kohn-Sham equation is founded on the Rajagopal-Callaway theorem, which is the relativistic expansion of the Hohenberg-Kohn theorem on the basis of QED (Rajagopal and Callaway 1973). In this theorem, two theorems are contained The first theorem proves that the four-component external potential, which is the vector-potential-extended external potential, is determined by the four-component current density, which is the current-density-extended electron density. On the other hand, the second theorem establishes the variational principle for every four-component current density. See Sect. 6.5 for vector potential and current density. Consequently, the solution of the Dirac-Kohn-Sham equation is represented by the four-component orbital. This four-component orbital is often called a molecular spinor. However, this name includes no indication of orbital, which is the solution of one-electron SCF equations moreover, the targets of the calculations are not restricted to molecules. Therefore, in this book, this four-component orbital is called an orbital spinor. The Dirac-Kohn-Sham wavefunction is represented by the Slater determinant of orbital spinors (see Sect. 2.3). Following the Roothaan method (see Sect. 2.5), orbital spinors are represented by a linear combination of the four-component basis spinor functions, Xp, ... 

The task of finding the single particle-like wavefunctions is now in principle equivalent to that within non-relativistic SIC-LSD theory. The four-component nature of the wavefunctions and the fact that neither spin nor orbital angular momentum are conserved separately presents some added technical difficulty, but this can be overcome using well-known techniques (Strange et al., 1984). The formal first-principles theory of MXRS, for materials with translational periodicity, is based on the fully relativistic spin-polarized SIC-LSD method in conjunction with second-order time-dependent perturbation theory (Arola et al., 2004). 

Thus one can solve the Dirac-Fock equation to obtain the relativistic energies and four-component spinor wavefunctions. 

Kim has formulated a relativistic Hartree-Fock-Roothaan equation for the ground states of closed-shell atoms using Slater-type orbitals. Relativistic effects in atoms have been reviewed by Grant. Malli and coworkers have formulated a relativistic SCF method for molecules. In this method, four-component spinor wavefunctions are obtained variationally in a self-consistent scheme using Gaussian basis sets. 

The solution of the Dirac-F ock equation is a set of four-component spinors. If the spinors are partitioned as core and valence spinors, then one can write the overall many-electron relativistic wavefunction for a single configuration as... 

As the Dirac operator thus contains 4x4 matrices, it is only meaningful to assume that the wavefunction is a 4-vector. In the following, we shall often refer to such a four-component, one-electron wavefunction as a spinor ... 

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