Fock-space Hamiltonian

The Fock-space Hamiltonian H is equivalent to the configuration-space Hamiltonian H insofar as both have the same matrix elements between n-electron Slater determinants. The main difference is that H has eigenstates of arbitrary particle number n it is, in a way, the direct sum of aU // . Another difference, of course, is that H is defined independently of a basis and hence does not depend on the dimension of the latter. One can also define a basis-independent Fock-space Hamiltonian H, in terms of field operators [11], but this is not very convenient for our purposes. 

Kutzelnigg and Koch/77/ also introduced a unitary Fock space cluster operator O = exp(o) with an antihermitian Fock space cr, as in eq. (7.2.3). In this case, the transformed Fock space hamiltonian L should be brought into a form such that... 

Substantial advantages are derived from the separable form of the electron interaction. Seven one-particle Hermitian matrices are required for the generation of the Hamiltonian in the present, reduced form. The matrices will be sparse and demand modest storage. Savings in storage become essential with increasing basis sets but even for the present case it is notable that seven 10-by-10 matrices has the data for the full 210-by-210 Fock space Hamiltonian. Symmetry and number conservation does reduce the number of non-vanishing matrix elements. 

In the A -electron case, we can write an effective Fock-space Hamiltonian... 

Note that the terms G and J are proportional to the single-particle density Pij — (V l W) of secondary reference state extended states A,B). The choice of this reference wavefunction is arbitrary for the algebraic properties of the extended wave-function and, in particular, for the derivation of the Dyson equation. Here it obviously introduces differences and the freedom of choice can be used to change the static self energy. The only condition that tp) has to comply with in order to have the full formalism at hand, is to be cm eigenfunction of the Fock-space Hamiltonian H (c. f. Sec. IIC). The two obvious choices for y )... 

The following formal definition of the space Y refers to a given choice of reference states %p) and fp) [as in Eq. (1)] that are proper eigenstates of a given Fock-space Hamiltonian H. The mathematical concepts used in this formal chapter can be found in common textbooks on functional anetlysis,... 

Let us now consider what physics is left out of the two electron Dirac equation of eq(7). To really describe the two body interaction, we should go to QED. QED starts with the one vertex interaction betweeg a field and a current the corresponding Fock space Hamiltonian is°... 

As a simple model, we confine our attention just to a single mode Ha(t) of the Hamiltonian (23). Note that neither any instantaneous eigenstate of Ha(t) is an exact quantum state nor e-/3ii W is a density operator. To calculate the thermal expectation value of an operator A, one needs either the Heisenberg operator Ah or the density operator pa(t) = UapaUa Now we use the time-dependent creation and annihilation operators (24), invariant operators, to construct the Fock space. 

We applied the Liouville-von Neumann (LvN) method, a canonical method, to nonequilibrium quantum phase transitions. The essential idea of the LvN method is first to solve the LvN equation and then to find exact wave functionals of time-dependent quantum systems. The LvN method has several advantages that it can easily incorporate thermal theory in terms of density operators and that it can also be extended to thermofield dynamics (TFD) by using the time-dependent creation and annihilation operators, invariant operators. Combined with the oscillator representation, the LvN method provides the Fock space of a Hartree-Fock type quadratic part of the Hamiltonian, and further allows to improve wave functionals systematically either by the Green function or perturbation technique. In this sense the LvN method goes beyond the Hartree-Fock approximation. 

The main idea of TFD is the following (Santana, 2004) for a given Hamiltonian which is written in terms of annihilation and creation operators, one applies a doubling procedure which implies extending the Fock space, formally written as Ht = H H. The physical variables are described by the non-tilde operators. In a second step, a Bogolyubov transformation is applied which introduces a rotation of the tilde and non-tilde variables and transforms the non-thermal variables into temperature-dependent form. This formalism can be applied to quite a large class of systems whose Hamiltonian operators can be represented in terms of annihilation and creation operators. 

Equation (4.1) is sometimes referred to as a state vector in Fock space and its use requires that the Hamiltonian be expressed in terms of operators that can act on such vectors. 

In (4.28) and (4.30), we have achieved our aim of expressing the Hamiltonian in the appropriate second quantized form for acting on the state vectors in Fock space. 

The definition of the pair part or, equivalently the no-pair part of Hmat is not unique. The precise meaning of no-pair implicitly depends on the choice of external potential, so that the operator Hm t depends implicitly on the external potential, whereas the sum Hmat Hm t + Hm t is independent of the choice of external potential. Since the no-pair part conserves the number of particles (electrons, positrons and photons) we can look for eigenstates of Hm j in the sector of Fock space with N fermions and no photons or positrons. Following Sucher [18,26,28], the resulting no-pair Hamiltonian in configuration space can be written as... 

By adopting the no-pair approximation, a natural and straightforward extension of the nonrelativistic open-shell CC theory emerges. The multireference valence-universal Fock-space coupled-cluster approach is employed [25], which defines and calculates an effective Hamiltonian in a low-dimensional model (or P) space, with eigenvalues approximating some desirable eigenvalues of the physical Hamiltonian. The effective Hamiltonian has the form [26]... 

In summary, Erdahl s treatment is more general and allows a more concise formulation because he works in Fock space, conserving only the parity of the number of particles however, he finds it necessary to restrict the coefficients to be real. We work at fixed particle number and have no reason for the restriction to real coefficients. If the Hamiltonian should be general Hermitian, in which case the RDM must likewise be assumed to be general Hermitian, then our approach leads to Hermitian semidefinite conditions. 

Energy levels of heavy and super-heavy (Z>100) elements are calculated by the relativistic coupled cluster method. The method starts from the four-component solutions of the Dirac-Fock or Dirac-Fock-Breit equations, and correlates them by the coupled-cluster approach. Simultaneous inclusion of relativistic terms in the Hamiltonian (to order o , where a is the fine-structure constant) and correlation effects (all products smd powers of single and double virtual excitations) is achieved. The Fock-space coupled-cluster method yields directly transition energies (ionization potentials, excitation energies, electron affinities). Results are in good agreement (usually better than 0.1 eV) with known experimental values. Properties of superheavy atoms which are not known experimentally can be predicted. Examples include the nature of the ground states of elements 104 md 111. Molecular applications are also presented. 

A. Landan, E. Ehav, and U. Kaldor, Intermediate Hamiltonian Fock-Space Coupled-Cluster Method and Applications. In R. F. Bishop, T. Brandes, K. A. Gernoth, N. R. Walet, and Y. Xian (Eds.) Recent Progress in Many-Body Theories, Advances in Quantum Many-Body Theories, Vol. 6. (World Scientific, Singapore, 2002), pp. 355-364 and references therein. 

Let us consider the 5s, 5p, 5d orbitals of lead and Is orbital of oxygen as the outercore and the ai, a2, os, tti, tt2 orbitals of PbO (consisting mainly of 6s, 6p orbitals of Pb and 2s, 2p orbitals of O) as valence. Although in the Cl calculations we take into account only the correlation between valence electrons, the accuracy attained in the Cl calculation of Ay is much better than in the RCC-SD calculation. The main problem with the RCC calculation was that the Fock-space RCC-SD version used there was not optimal in accounting for nondynamic correlations (see [136] for details of RCC-SD and Cl calculations of the Pb atom). Nevertheless, the potential of the RCC approach for electronic structure calculations is very high, especially in the framework of the intermediate Hamiltonian formulation [102, 131]. 

A. Landau, E. Eliav, U. Kaldor, Intermediate Hamiltonian Fock-space coupled-cluster method, Chem. Phys. Lett. 313 (1999) 399. 

Kutzelnigg/76/ and Kutzelnigg and Koch/77/ emphasized that the classification of the operators into the categories C, A, B and 0 is essentially a Fock space concept, so that the condition that L, vanishes will automativally generate operator equivalent of the eq. (7.1.3). L, is then the Fock-space effective hamiltonian H, and appropriate... 

Successful model building is at the very heart of modern science. It has been most successful in physics but, with the advent of quantum mechanics, great inroads have been made in the modelling of various chemical properties and phenomena as well, even though it may be difficult, if not impossible, to provide a precise definition of certain qualitative chemical concepts, often very useful ones, such as electronegativity, aromaticity and the like. Nonetheless, all successful models are invariably based on the atomic hypothesis and quantum mechanics. The majority, be they of the ah initio or semiempirical type, is defined via an appropriate non-relativistic, Born-Oppenheimer electronic Hamiltonian on some finite-dimensional subspace of the pertinent Hilbert or Fock space. Consequently, they are most appropriately expressed in terms of the second quantization formalism, or even unitary group formalism (see, e.g. [33]). 

L. Meissner and R. J. Bartlett, J. Chem. Phys., 94, 6670 (1991). Transformation of the Hamiltonian in Excitation Energy Calculations Comparison Between Fock-Space Multireference Coupled-Cluster and Equation-of-Motion Coupled-Cluster Methods. 

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