Spinors four-component

Section VI shows the power of the modulus-phase formalism and is included in this chapter partly for methodological purposes. In this formalism, the equations of continuity and the Hamilton-Jacobi equations can be naturally derived in both the nonrelativistic and the relativistic (Dirac) theories of the electron. It is shown that in the four-component (spinor) theory of electrons, the two exha components in the spinor wave function will have only a minor effect on the topological phase, provided certain conditions are met (nearly nonrelativistic velocities and external fields that are not excessively large). 

Here, v / is a four-component spinor, is a four potential, and the 4x4 matrices 7 are given by... 

In this paper, for functions (pi r) we shall use the four-component spinors r) being solutions of the Dirac equation... 

The proof takes different forms in different representations. Here we assume that quantum states are column vectors (or spinors ) iji, with n elements, and that the scalar product has the form ft ip. If ip were a Schrodinger function, J ftipdr would take the place of this matrix product, and in Dirac s theory of the electron, it would be replaced by J fttpdr, iji being a four-component spinor. But the work goes through as below with only formal changes. Use of the bra-ket notation (Chapter 8) would cover all these cases, but it obscures some of the detail we wish to exhibit here. 

Since Eq. (10-391) is a second-order equation for the four-component spinor , it will have twice as many solutions as Eq. (10-389), the solutions of which we are interested in obtaining. Equation (10-391) can be further simplified by multiplying out the two bracketed factors... 

This non-relativistic equation in terms of four-component spinors has been studied in detail by Levy-Leblond [44,45], who has shown that it results automatically from a study of the irreducible representations of the Gahlei group and that it gives a correct description of spin. It is easy to see that in the absence of an external magnetic field, equation (63) is equivalent to the Schrodinger equation in the sense that after elimination of the small component ... 

Table I also contains an analysis of the orbital character of these five energy levels. These were determined from the four-component spinors by neglecting the two lower, "small," components, and by assuming that the radial functions depend only upon , i.e. that the radial functions for pi/2 and p3/2> or for da/2 and ds/2> are the same. The orbitals may then be written in "Pauli" form as products of (complex) spherical harmonics and spin functions. Populations are equal to the squares of the absolute magnitudes of the coefficients listed in Table I. [For all but 17e3g, an additional orbital (not shown) is occupied which has the same energy but the opposite spin pattern (i.e. a and 3 are interchanged).]...

Heavy atoms exhibit large relativistic effects, often too large to be treated perturba-tively. The Schrodinger equation must be supplanted by an appropriate relativistic wave equation such as Dirac-Coulomb or Dirac-Coulomb-Breit. Approximate one-electron solutions to these equations may be obtained by the self-consistent-field procedure. The resulting Dirac-Fock or Dirac-Fock-Breit functions are conceptually similar to the familiar Hartree-Fock functions the Hartree-Fock orbitals are replaced, however, by four-component spinors. Correlation is no less important in the relativistic regime than it is for the lighter elements, and may be included in a similar manner. 

Here frs and (ri-l tM> are, respectively, elements of one-electron Dirac-Fock and antisymmetrized two-electron Coulomb-Breit interaction matrices over Dirac four-component spinors. The effect of the projection operators is now taken over by the normal ordering, denoted by the curly braces in (15), which requires annihilation operators to be moved to the right of creation operators as if all anticommutation relations vanish. The Fermi level is set at the top of the highest occupied positive-energy state, and the negative-energy states are ignored. 

Abstract. Investigation of P,T-parity nonconservation (PNC) phenomena is of fundamental importance for physics. Experiments to search for PNC effects have been performed on TIE and YbF molecules and are in progress for PbO and PbF molecules. For interpretation of molecular PNC experiments it is necessary to calculate those needed molecular properties which cannot be measured. In particular, electronic densities in heavy-atom cores are required for interpretation of the measured data in terms of the P,T-odd properties of elementary particles or P,T-odd interactions between them. Reliable calculations of the core properties (PNC effect, hyperfine structure etc., which are described by the operators heavily concentrated in atomic cores or on nuclei) usually require accurate accounting for both relativistic and correlation effects in heavy-atom systems. In this paper, some basic aspects of the experimental search for PNC effects in heavy-atom molecules and the computational methods used in their electronic structure calculations are discussed. The latter include the generalized relativistic effective core potential (GRECP) approach and the methods of nonvariational and variational one-center restoration of correct shapes of four-component spinors in atomic cores after a two-component GRECP calculation of a molecule. Their efficiency is illustrated with calculations of parameters of the effective P,T-odd spin-rotational Hamiltonians in the molecules PbF, HgF, YbF, BaF, TIF, and PbO. 

All the above restoration schemes are called nonvariational as compared to the variational one-center restoration (VOCR, see below) procedure proposed in [79, 80]. Proper behavior of the molecular orbitals (four-component spinors) in atomic cores of molecules can be restored in the scope of a variational procedure if the molecular pseudoorbitals (two-component pseudospinors) match correctly the original orbitals (large components of bispinors) in the valence region after the molecular RECP calculation. As is demonstrated in [69, 44], this condition is rather correct when the shape-consistent RECP is involved to the molecular calculation with explicitly... 

Generation of equivalent basis sets of one-center four-component spinors fnljiy)Xljm... 

Finally, the atomic two-component pseudospinors in the molecular basis are replaced by equivalent four-component spinors and the expansion coefficients from Eq. (6.3) are preserved ... 

The molecular four-component spinors constructed this way are orthogonal to the inner core spinors of the atom, because the atomic basis functions used in Eq. (6.4) are generated with the inner core shells treated as frozen. 

Two-step calculation of molecular properties. To evaluate one-electron core properties (hyperfine structure, P,T-odd effects etc.) employing the above restoraton schemes it is sufficient to obtain the one-particle density matrix, Dpq, after the molecular RECP calculation in the basis of pseudospinors p. At the same time, the matrix elements Wpq of a property operator W(x) should be calculated in the basis of equivalent four-component spinors p. The mean value for this operator can be then evaluated as ... 

Relativity becomes important for elements heavier than the first row transition elements. Most methods applicable on molecules are derived from the Dirac equation. The Dirac equation itself is difficult to use, since it involves a description of the wave function as a four component spinor. The Dirac equation can be approximately brought to a two-component form using e.g. the Foldy-Wouthuysen (FW) transformational,12]. Unfortunately the FW transformation, as originally proposed, is both quite complicated and also divergent in the expansion in the momentum (for large momenta), and it can thus only be carried out approximately (usually to low orders). The resulting equations are not variationally stable, and they are used only in first order perturbation theory. 

Thus, the non-relativistic wave function (1.14) of an electron is a two-component spinor (tensor having half-integer rank) whereas its relativistic counterpart is already, due to the presence of large (/) and small (g) components, a four-component spinor. The choice of / in the form (1 + l — l ) is conditioned by the requirement of a standard phase system for the wave functions (see Introduction, Eq. (4)). 

The energy spectrum of atoms and ions with j j coupling can be found using the relativistic Hamiltonian of iV-electron atoms (2.1)-(2.7). Its irreducible tensorial form is presented in Chapter 19. The relativistic one-electron wave functions are four-component spinors (2.15). They are the eigenfunctions of the total angular momentum operator for the electron and are used to determine one-electron and two-electron matrix elements of relativistic interaction operators. These matrix elements, in the representation of occupation numbers, are the parameters that enter into the expansions of the operators corresponding to physical quantities (see general expressions (13.22) and (13.23)). 

The wave function P=P(R, t) may be written as a four-component spinor... 

On the other hand, in the pioneering DHF and post-DHF program package MOLFDIR [3] and the well-developed four-component relativistic program package DIRAC [4], the molecular four-component spinors are expanded into decoupled... 

It is convenient to write the four-component spinor ip) as two two-component spinors... 

The coupled radial equations (4.185) are the relativistic analogue of (4.19) for bound states and (4.57) for scattering states. In order to set up partial-wave integral equations corresponding to (4.121) we need the partial-wave form of the free-electron state (3.170). This is set up by generalising (4.56) to include the spin and using it in the partial-wave expansion of (3.170), which becomes a four-component spinor. 

The integral equations for relativistic potential scattering are conveniently written in terms of a four-dimensional notation for the four-component spinor vp). 

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 . 

In principle, all four-component molecular electronic structure codes work like their nonrelativistic relatives. This is, of course, due to the formal similarity of the theories where one-electron Schrbdinger operators are replaced by four-component Dirac operators enforcing a four-component spinor basis. Obviously, the spin symmetry must be treated in a different way, i.e. it is replaced by the time-reversal symmetry being the basis of Kramers theorem. Point group symmetry is replaced by the theory of double groups, since spatial and spin coordinates cannot be treated separately. 

---