Many Electron Relativistic Hamiltonian

A systematic development of relativistic molecular Hamiltonians and various non-relativistic approximations are presented. Our starting point is the Dirac one-fermion Hamiltonian in the presence of an external electromagnetic field. The problems associated with generalizing Dirac s one-fermion theory smoothly to more than one fermion are discussed. The description of many-fermion systems within the framework of quantum electrodynamics (QED) will lead to Hamiltonians which do not suffer from the problems associated with the direct extension of Dirac s one-fermion theory to many-fermion system. An exhaustive discussion of the recent QED developments in the relevant area is not presented, except for cursory remarks for completeness. The non-relativistic form (NRF) of the many-electron relativistic Hamiltonian is developed as the working Hamiltonian. It is used to extract operators for the observables, which represent the response of a molecule to an external electromagnetic radiation field. In this study, our focus is mainly on the operators which eventually were used to calculate the nuclear magnetic resonance (NMR) chemical shifts and indirect nuclear spin-spin coupling constants. 

One of the major fundamental difference between nonrelativistic and relativistic many-electron problems is that while in the former case the Hamiltonian is explicitly known from the very beginning, the many-electron relativistic Hamiltonian has only an implicit form given by electrodynamics [13,37]. The simplest relativistic model Hamiltonian is considered to be given by a sum of relativistic (Dirac) one-electron Hamiltonians ho and the usual Coulomb interaction term ... 

The relativistic DVME method 3.2.1. The many-electron Dirac Hamiltonian... 

The electric-dipole transition is determined by the symmetry properties of the initial-state and the final-state wave functions, i.e., their irreducible representations. In the case of electric-dipole transitions, the selection rules shown in table 7 hold true (n and a represent the polarizations where the electric field vector of the incident light is parallel and perpendicular to the crystal c axis, respectively. Forbidden transitions are denoted by the x sign). In the relativistic DVME method, the Slater determinants are symmetrized according to the Clebsch-Gordan coefficients and the symmetry-adapted Slater determinants are used as the basis functions. Therefore, the diagonalization of the many-electron Dirac Hamiltonian is performed separately for each irreducible representation. 

By an apphcation of the DK transformation to the relativistic many-electron Hamiltonian, recently, we have shown that the many-electron DK Hamiltonian also gives satisfactory results for a wide variety of atoms and molecules compared with... 

An alternative approach to the perturbation theory in treating many-electron systems is the configuration-interaction (Cl) method which is based on the variational principle. Nonrelativistic Cl techniques have been used extensively in atomic and molecular calculations. The generalization to relativistic configuration-interaction (RCI) calculations, however, presents theoretical as well as technical challenges. The problem originates from the many-electron Dirac Hamiltonian commonly used in RCI calculations ... 

The derivation of the ZORA approach is valid only for the one-electron Dirac equation with an external potential. Thus, the theory must be extended in order to obtain the relativistic many-electron ZORA Hamiltonian with the electron-electron Coulomb or Breit interaction. The many-electron ZORA Hamiltonian may be defined in several ways. In the present study, we neglect the relativistic kinematics correction to the electron-electron interaction, which yields the simplest many-electron ZORA Hamiltonian, that is, the one-electron ZORA Hamiltonian with the electron-electron Coulomb operator in the non-relativistic form,... 

We have already discussed in chapters 12 and 13 that low-order scalar-relativistic operators such as DKH2 or ZORA provide very efficient variational schemes, which comprise all effects for which the (non-variational) Pauli Hamiltonian could account for (as is clear from the derivations in chapters 11 and 13). It is for this reason that historically important scalar relativistic corrections which can only be considered perturbatively (such as the mass-velocity and Darwin terms in the Pauli approximation in section 13.1), are no longer needed and their significance fades away. There is also no further need to develop new pseudo-relativistic one- and two-electron operators. This is very beneficial in view of the desired comparability of computational studies. In other words, if there were very many pseudo-relativistic Hamiltonians available, computational studies with different operators of this sort on similar molecular systems would hardly be comparable. 

The relativistic Hamilton operator for an electron can be derived, using the correspondence principle, from its relativistic classical Hamiltonian and this leads to the one-electron Dirac equation, which does contain spin operators. From the one-electron Dirac equation it seems trivial to define a many-electron relativistic equation, but the generalization to more electrons is less straightforward than in the non-relativistic case, because the electron-electron interaction is not unambiguously defined. The non-relativistic Coulomb interaction is often used as a reasonable first approximation. The relativistic treatment of atoms and molecules based on the many-electron Dirac equation leads to so-called four-component methods. The name stems from the fact that the electronic wave functions consist of four instead of two components. When the couplings between spin and orbital angular moment are comparable to the electron-electron interactions this is the preferred way to explain the electronic structure of the lowest states. 

The relativistic many-electron Hamiltonian cannot be written in closed form it may be derived perturbatively from quantum electrodynamics [1]. The simplest form is the Dirac-Coulomb (DC) Hamiltonian, where the nonrelativistic one-electron terms in the Schrodinger equation are replaced by the one-electron Dirac operator hj). 

The no-pair DCB Hamiltonian (6) is used as a starting point for variational or many-body relativistic calculations [9], The procedure is similar to the nonrelativistic case, with the Hartree-Fock orbitals replaced by the four-component Dirac-Fock-Breit (DFB) functions. The spherical symmetry of atoms leads to the separation of the one-electron equation into radial and spin-angular parts [10], The radial four-spinor has the so-called large component the upper two places and the small component Q, in the lower two. The quantum number k (with k =j+ 1/2) comes from the spin-angular equation, and n is the principal quantum number, which counts the solutions of the radial equation with the same k. Defining... 

Neglecting spin-orbit contributions (smaller than other relativistic corrections for the ground state of atoms, and zero for closed-shell ones), the Breit hamiltonian in the Pauli approximation [25] (weak relativistic systems) can be written for a many electron system as ... 

We demonstrated that by the selection of a representation of the Dirac Hamiltonian in the spinor space one may strongly influence the performance of the variational principle. In a vast majority of implementations the standard Pauli representation has been used. Consequently, computational algorithms developed in relativistic theory of many-electron systems have been constructed so that they are applicable in this representation only. The conditions, under which the results of these implementations are reliable, are very well understood and efficient numerical codes are available for both atomic and molecular calculations (see e.g. [16]). However, the representation of Weyl, if the external potential is non-spherical, or the representation of Biedenharn, in spherically-symmetric cases, seem to be attractive and, so far, hardly explored options. 

A. Relativistic Semi-Classical Many-Electron Hamiltonian 180... 

The third term in Eq. (8) is the sum over all electron-electron repulsion operators abbreviated by g(i,j), which is in the case of the relativistic many-electron Hamiltonian equal to... 

In order to improve the theoretical description of a many-body system one has to take into consideration the so-called correlation effects, i.e. to deal with the problem of accounting for the departures from the simple independent particle model, in which the electrons are assumed to move independently of each other in an average field due to the atomic nucleus and the other electrons. Making an additional assumption that this average potential is spherically symmetric we arrive at the central field concept (Hartree-Fock model), which forms the basis of the atomic shell structure and the chemical regularity of the elements. Of course, relativistic effects must also be accounted for as corrections, if they are small, or already at the very beginning starting with the relativistic Hamiltonian and relativistic wave functions. 

While using (4.14) and exact wave functions. This supports the conclusion of Drake [83] that for electric dipole transitions, by considering the commutator of with the atomic Hamiltonian in the Pauli approximation, we obtain Qwith relativistic corrections of order v2/c2 (see (4.18)-(4.20)). However, for many-electron atoms and ions, one has to use approximate (e.g., Hartree-Fock) wave functions, and then this term gives non-zero contribution, conditioned by the inaccuracy of the model adopted. 

Thus, we have expressed the non-relativistic Hamiltonian of a many-electron atom with relativistic corrections of order a2 in the framework of the Breit operator (formulas (1.15), (1.18)—(1.22)) in terms of the irreducible tensorial operators (second term in (1.15), formulas (19.5)—(19.8), (19.10)— (19.14), (19.20), respectively). 

In non-relativistic perturbative atomic Z-expansion theory, as recently sum-marked [11], a new scaled length, p = Zr, and a scaled energy, e= T2 E, are introduced in the many-electron wave equation. That is, the units of length and energy are changed to 1/Z and Z2 a.u., respectively. The Hamiltonian then takes the form... 

Unimolecular reactions can, of course, also be induced by UV-laser pulses. As pointed out above, in order to reach a specific reaction channel, the electric field of the laser pulse must be specifically designed to the molecular system. All features of the system, i.e., the Hamiltonian (including relativistic terms), must be completely known in order to solve this problem. In addition, the full Schrodinger equation for a large molecular system with many electrons and nuclei can at present only be solved in an approximate way. Thus, in practice, the precise form of the laser field cannot always be calculated in advance. 

Since the Dirac equation is written for one electron, the real problem of ah initio methods for a many-electron system is an accurate treatment of the instantaneous electron-electron interaction, called electron correlation. The latter is of the order of magnitude of relativistic effects and may contribute to a very large extent to the binding energy and other properties. The DCB Hamiltonian (Equation 3) accounts for the correlation effects in the first order via the Vy term. Some higher order of magnitude correlation effects are taken into account by the configuration interaction (Cl), the many-body perturbation theory (MBPT) and by the presently most accurate coupled cluster (CC) technique. 

An efficient way to solve a many-electron problem is to apply relativistic effective core potentials (RECP). According to this approximation, frozen inner shells are omitted and replaced in the Hamiltonian hnt by an additional term, a pseudopotential (UREP)... 

In the DVME method, the many-electron Hamiltonian is diagonalized based on the Cl approach. In this approach, the Zth many-electron wave function Fi is represented as a linear combination of the Slater determinants which are constructed from MOs obtained by the relativistic DV-Xa calculations as ... 

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. 

It is possible to extend Dirac s (7.) relativistic theory for the hydrogen atom to n-electron systems by neglecting retardation as well as certain magnetic effects.Dirac s Hamiltonian for a many electron system can be written as... 

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