Dirac-Hartree-Fock theory

Accounting for relativistic effects in computational organotin studies becomes complicated, because Hartree-Fock (HF), density functional theory (DFT), and post-HF methods such as n-th order Mpller-Plesset perturbation (MPn), coupled cluster (CC), and quadratic configuration interaction (QCI) methods are non-relativistic. Relativistic effects can be incorporated in quantum chemical methods with Dirac-Hartree-Fock theory, which is based on the four-component Dirac equation. " Unformnately the four-component Flamiltonian in the all-electron relativistic Dirac-Fock method makes calculations time consuming, with calculations becoming 100 times more expensive. The four-component Dirac equation can be approximated by a two-component form, as seen in the Douglas-Kroll (DK) Hamiltonian or by the zero-order regular approximation To address the electron cor-... 

The Slater determinant represents the simplest approximation to an electronic ground state, and its orbitals may be optimized to approximate the ground state as closely as possible within the independent particle model. We shall see later in this chapter how the optimization of the orbitals can be done within (Dirac-)Hartree-Fock theory by relying on the variational principle. 

In approximate Cl methods, the set of many-particle basis functions is restricted and not infinitely large, i.e., it is not complete. Then, the many-particle basis is usually constructed systematically from a given reference basis function. (such as the Slater determinant, which is constructed to approximate the ground state of a many-electron system in (Dirac-)Hartree-Fock theory). 

In accordance with the equivalence restriction a shell is classified by one pair of quantum numbers n and k. A shell comprises 2 k atomic spinors and is therefore 2 x -fold degenerate. A closed shell is characterized by the fact that all of these degenerate spinors enter the single Slater determinant in Dirac-Hartree-Fock theory. 

Comparison of Atomic Hartree-Fock and Dirac-Hartree-Fock Theories... 

However, the short-range behavior of the inhomogeneous part Xf r)/Ri r) (with R being S,P, Q and R, the corresponding radial function) of the electron-electron interaction potentials is different in nonrelativistic and relativistic theory because of the exponents in the series expansions of the radial functions, Eqs. (9.167) and (9.168). This difference has its origin in the structure of the differential equations Eq. (9.120), which are of second order, and Eq. (9.122), which are coupled first-order differential equations. The way in which the structure of the differential equations determines the exponents in the radial function s series expansions has been shown above. In the case of Dirac-Hartree-Fock theory, these exponents additionally depend on the type... 

The development of MOLFDIR came to an end in 2001 and some of the developers of this program joined forces with a new Scandinavian program, Dirac, that emerged in the mid 1990s [518]. Dirac contains an elegant implementation of Dirac-Hartree-Fock theory as a direct SCF method [317] in terms of quaternion algebra [318,319]. For the treatment of electron correla-... 

In the preceding chapter on isolated, spherically symmetric atoms, we chose to derive Cl and SCF equations from the most general expression of the total electronic energy in which the total state is expanded in a CSF many-particle basis set. Here, we could proceed in the same way but start instead with the simple Dirac-Hartree-Fock theory for the sake of convenience. Its extension we discuss later in this chapter. 

Hence, the relativistic analog of the spin-restriction in nonrelativistic closed-shell Hartree-Fock theory is Kramers-restricted Dirac-Hartree-Fock theory. We should emphasize that our derivation of the Roothaan equation above is the pedestrian way chosen in order to produce this matrix-SCF equation step by step. The most sophisticated formulations are the Kramers-restricted quaternion Dirac-Hartree-Fock implementations [286,318,319]. A basis of Kramers pairs, i.e., one adapted to time-reversal s)mimetry, transforms into another basis under quatemionic unitary transformation [589]. This can be exploited not only for the optimization of Dirac-Hartree-Fock spinors, but also for MCSCF spinors. In a Kramers one-electron basis, an operator O invariant under time reversal possesses a specific block structure. 

So far, we have only discussed the four-component basis-set approach in connection with the simplest ab initio wave-function model, namely for a single Slater determinant provided by Dirac-Hartree-Fock theory. We know, however, from chapter 8 how to improve on this model and shall now discuss some papers with a specific focus on correlated four-component basis-set methods. 

S. N. Datta and C. E. Ewig, Chem. Phys. Lett., 85,443 (1982). Dirac-Hartree-Fock Theory and Computational Procedure for Molecules. 

So far we have not taken time-reversal symmetry into account. From the preceding chapters, we expect that incorporating time-reversal symmetry in a Kramers-restricted Dirac-Hartree-Fock theory will result in a reduction of the work, and possibly also a reduction in the rank of the Fock matrix. The basis set we will use is a basis set of Kramers pairs. We develop the theory for a closed-shell reference, for which all Kramers pairs are doubly occupied. ... 

The Dirac equation can be readily adapted to the description of one electron in the held of the other electrons (Hartree-Fock theory). This is called a Dirac-Fock or Dirac-Hartree-Fock (DHF) calculation. 

The time-dependent Hartree-Fock theory was first discussed by Dirac (1930b) and subsequently in perturbative form by Dalgamo and Victor (1966). Its relationship to time-dependent perturbation theory has been discussed by Langhoff, Epstein and Karplus (1972). 

As an approach analogous of nonrelativistic Hartree-Fock theory, the four-component Dirac-Hartree-Fock wave function is described with a Slater determinant of one-electron molecular functions ( aX l= U Nelec, ... 

It has recently been shown [ 12] that time-dependent or linear-response theory based on local exchange and correlation potentials is inconsistent in the pure exchange limit with the time-dependent Hartree-Fock theory (TDHF) of Dirac [13] and with the random-phase approximation (RPA) [14] including exchange. The DFT-based exchange-response kernel [15] is inconsistent with the structure of the second-quantized Hamiltonian. 

Aspects of the relativistic theory of quantum electrodynamics are first reviewed in the context of the electronic structure theory of atoms and molecules. The finite basis set parametrization of this theory is then discussed, and the formulation of the Dirac-Hartree-Fock-Breit procedure presented with additional detail provided which is specific to the treatment of atoms or molecules. Issues concerned with the implementation of relativistic mean-field methods are outlined, including the computational strategies adopted in the BERTHA code. Extensions of the formalism are presented to include open-shell cases, and the accommodation of some electron correlation effects within the multi-configurational Dirac-Hartree-Fock approximation. We conclude with a survey of representative applications of the relativistic self-consistent field method to be found in the literature. 

The relativistic theory and computation of atomic structures and processes has therefore attained some sort of maturity and the various codes now available are widely used. Those mentioned so far were based on ideas originating from Hartree and his students [28], and have been developed in much the same way as the non-relativistic self-consistent field theory recorded in [28-30]. All these methods rely on the numerical solution, using finite differences, of the coupled differential equations for radial orbital wave-functions of the self-consistent field. This makes them unsuitable for the study of molecules, for which it is preferable to expand the radial amplitudes in a suitably chosen set of analytic functions. This nonrelativistic matrix Hartree-Fock method, as it is often termed, was pioneered by Hall and Lennard-Jones [31], Hall [32,33] and Roothaan [34,35], and it was Roothaan s students, Synek [36] and Kim [37] who were the first to attempt to solve the corresponding matrix Dirac-Hartree-Fock equations. Kim was able to obtain solutions for the ground state of neon in 1967, but at the expense of some numerical instability, and it seemed at the time that the matrix Dirac-Hartree-Fock scheme would not be a serious competitor to the finite difference codes. 

Dirac s relativistic theory for the motion of electrons in molecules was introduced in the preceding chapters. The appearance of positron solutions and the four-component form of the wave function looks problematic at first sight but in practice it turns out that the real challenge is, like in non-relativistic electronic structure theory, the description of the correlation between the motion of electrons. The mean-field approximation that is made in the Dirac-Hartree-Fock (DHF) approach provides a good first step, but gives bond energies and structures that are often too inaccurate for chemical purposes. 

The final group in the chain should be Abelian and is used at the Cl level of theory, while the first and highest group can be used at the Dirac-Hartree-Fock level of theory where inclusion of non-Abelian symmetry is easier. 

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