Standard approaches to approximating solutions to the Schroedinger equation rely upon the assumption that there is a single dominant electronic configuration with a small number of low-lying excited states. As such, they are referred to as single reference approaches and are accurate only when the band gap is small in comparison with the inter-electronic repulsion of the valence electrons. Systems for which this is the case are weakly-correlated. If the inter-electronic repulsion larger than the band gap, then a single electronic reference is not an appropriate ansatz for the physical wavefunction. As the strength of the interaction is increased many Slater determinants become near-degenerate, each providing non-negligible contributions. Such systems are strongly-correlated. The goal of the thesis was to employ wavefunctions which are: non-trivial, tractable, size-consistent and extensive, and not given in an active space. We have outlined approaches based on wavefunction forms more suited to describe strong correlation. Built on the Lie algebra su(2), our first trial wavefunction was the Bethe ansatz solution to the reduced BCS Hamiltonian derived by Richardson. This wavefunction is expressed as a product of quasi-particles each parametrized in terms of quasi-momenta. Consistency among the quasi-momenta is ensured by a set of non-linear equations to be solved numerically. This approach is feasible in both variational and projected flavours. We next considered a wavefunction of the same form without requiring it to be an eigenvector of the reduced BCS Hamiltonian. A variational approach in this case is only feasible provided there are two equivalent descriptions in terms of particles and holes. In any case, a bivariational principle and a projected approach are both feasible. Also based on su(2), there is AP1roG (coupled cluster pair doubles). Open-shell singlets and triplets were constructed with the Lie algebras sp(N) and so(4N). The resulting formulae appear to be infeasible unless it is possible to efficiently compute generalizations of determinants to three-dimensional objects. Treating each spatial orbital individually, all four possible occupations close the Lie superalgebra gl(2|2).
A general Hamiltonian H of electrons in finite concentration, interacting via any two-body coupling inside a crystal of arbitrary dimension, is considered. For simplicity and without loss of generality, a one-band model is used to account for the electron-crystal interaction. The electron motion is described in the Hilbert space ${\mathit{S}}_{\mathrm{\ensuremath{\varphi}}}$, spanned by a basis of Slater determinants of one-electron Bloch wave functions. Electron pairs of total momentum K and projected spin \ensuremath{\zeta}=0,\ifmmode\pm\else\textpm\fi{}1 are considered in this work. The Hamiltonian then reads H=
HD+${\ensuremath{\sum}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$${\mathit{H}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$, where
HD consists of the diagonal part of H in the Slater determinant basis. ${\mathit{H}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$ describes the off-diagonal part of the two-electron scattering process which conserves K and \ensuremath{\zeta}. This Hamiltonian operates in a subspace of ${\mathit{S}}_{\mathrm{\ensuremath{\varphi}}}$, where the Slater determinants consist of pairs characterized by the same K and \ensuremath{\zeta}. It is shown that the whole set of eigensolutions \ensuremath{\psi},\ensuremath{\epsilon} of the time-independent Schr\"odinger equation (H-\ensuremath{\epsilon})\ensuremath{\psi}=0 divides into two classes, ${\mathrm{\ensuremath{\psi}}}_{1}$,${\mathrm{\ensuremath{\epsilon}}}_{1}$ and ${\mathrm{\ensuremath{\psi}}}_{2}$,${\mathrm{\ensuremath{\epsilon}}}_{2}$. The eigensolutions of class 1 are characterized by the property that for each solution ${\mathrm{\ensuremath{\psi}}}_{1}$,${\mathrm{\ensuremath{\epsilon}}}_{1}$ there is a single K and \ensuremath{\zeta} such that (
HD+${\mathit{H}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$-${\mathrm{\ensuremath{\epsilon}}}_{1}$)${\mathrm{\ensuremath{\psi}}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$=0 where, in general, ${\mathrm{\ensuremath{\psi}}}_{1}$\ensuremath{\ne}${\mathrm{\ensuremath{\psi}}}_{\mathit{K},\mathrm{\ensuremath{\zeta}}}$, whereas each solution ${\mathrm{\ensuremath{\psi}}}_{2}$,${\mathrm{\ensuremath{\epsilon}}}_{2}$ of class 2 fulfills (
HD-${\mathrm{\ensuremath{\epsilon}}}_{2}$)${\mathrm{\ensuremath{\psi}}}_{2}$=0. We prove also that the eigenvectors of class 1 have off-diagonal long-range order, whereas those of class 2 do not. Finally, our result shows that off-diagonal long-range order is not a sufficient condition for superconductivity. \textcopyright{} 1996 The American Physical Society.
The method of correlated basis functions provides a means of systematically exploiting our intuitive understanding of real physical systems. Here we seek especially to develop a formalism for describing systems of strongly interacting fermions, for example, nuclei and liquid
He3, using a complete set of correlated functions ${\ensuremath{\Psi}}_{\mathrm{m}}=\frac{F{\ensuremath{\Phi}}_{\mathrm{m}}}{{({\ensuremath{\Phi}}_{\mathrm{m}}, {F}^{2}{\ensuremath{\Phi}}_{\mathrm{m}})}^{\frac{1}{2}}}$.
F is taken as a product of two-body factors, $\ensuremath{\Pi}{i<j}^{}[f({r}_{\mathrm{ij}})]$, the
f(rij) embodying at least the correlations arising from strong short-range repulsions; and ${{\ensuremath{\Phi}}_{\mathrm{m}}}$, a set of independent-particle-model functions which might serve as a basis in the absence of highly singular interactions. The matrix elements
Hmn,
Nmn of the Hamiltonian and identity operators with respect to the correlated basis ${{\ensuremath{\Psi}}_{\mathrm{m}}}$ are evaluated by generalization of cluster-expansion techniques developed originally for the calculation of the partition function of a classical imperfect gas and adapted to the quantum-mechanical many-body problem by Iwamoto and Yamada. Contributions to our expansions for the
Hmn are classified according to order of magnitude in the quantity $\ensuremath{\rho}\ensuremath{\omega}$, where $\ensuremath{\omega}=\ensuremath{\int}({f}^{2}(r)\ensuremath{-}1)d\mathrm{r}$ is a "correlation parameter" and $\ensuremath{\rho}$ the average particle density. To the extent that $|\ensuremath{\rho}\ensuremath{\omega}|$ is small, it provides a true expansion parameter. A detailed technical discussion of the cluster expansions is given, with special emphasis on their symmetry properties upon truncation. Although the many-body problem is soluble by simultaneous diagonalization of the matrices (
Hmn) and (
Nmn), it is preferable first to transform to an orthonormal basis of "unperturbed" correlated functions ${{\ensuremath{\Theta}}_{\mathrm{m}}}$ with respect to which the Hamiltonian and identity operators have the matrix representations (
Hmn) and $({N}_{\mathrm{mn}})=({\ensuremath{\delta}}_{\mathrm{mn}})$, and then to attempt the separate diagonalization of (
Hmn). In general, such a transformation is expedited by the L\"owdin procedure carried out to the desired order in $\ensuremath{\rho}\ensuremath{\omega}$. However, a Schmidt orthogonalization scheme might prove more advantageous in specific cases. Field-theoretic techniques (of both perturbative and nonperturbative nature) may be brought to bear in the diagonalization of (
Hmn). The inverse of the unitary transformation which takes the basis ${{\ensuremath{\Phi}}_{\mathrm{m}}}$ into the basis ${{\ensuremath{\Theta}}_{\mathrm{m}}}$, applied to the given singular Hamiltonian, leads---for any
F in the class considered---to a non-singular "effective Hamiltonian." Following this formal cue, we set out to construct explicitly a second-quantized effective Hamiltonian which generates the same matrix elements, to prescribed order in $\ensuremath{\rho}\ensuremath{\omega}$, when operating between independent-particle kets of the model occupation-number representation, as does the given Hamiltonian in the configuration-space representation, between the corresponding correlated functions of the L\"owdin basis. The quasiparticles described by this effective Hamiltonian interact via well-behaved two-body, three-body, \ifmmode\cdot\else\textperiodcentered\fi{}\ifmmode\cdot\else\textperiodcentered\fi{}\ifmmode\cdot\else\textperiodcentered\fi{},
Q-body, \ifmmode\cdot\else\textperiodcentered\fi{}\ifmmode\cdot\else\textperiodcentered\fi{}\ifmmode\cdot\else\textperiodcentered\fi{} potentials, in contrast to the highly singular two-body interactions of the real particles. For small $|\ensuremath{\rho}\ensuremath{\omega}|$, the effective two-body forces predominate. An avenue to deeper understanding of the applicability of the nuclear-shell model and the dressed-quasiparticle theory of liquid
He3 has been opened. This article treats only the formalism for a uniform extended medium. Numerical calculations, as well as the extension of the method to finite systems, will follow.
This work is mainly devoted to the description of processes that involve the interaction between an atom and a surface, in which a strong Coulomb repulsion on the atomic site
(U) limits the charge exchange to one electron (infinite-
U limit). In this limit, the Anderson Hamiltonian for a many-fold
(N) of states localized on the atomic site can be represented in terms of auxiliary bosons and physical operators in the mixed boson-electron space can be defined. In this work the Hamiltonian is solved by defining appropriate Green's functions for physical operators. Then we solved the equations of motion of these Green's functions, up to a second order in the atom-surface coupling, either for the stationary case or for a real time-dependent problem. We show that our approach reproduces the known exact results in the nondegenerate
(N=1) case, and for $N\ensuremath{\succ}1$ gives excellent agreement with exact calculations and approximations valid for large
N (the
1∕N expansion). Finally, the accurate description of dynamical processes is shown by the comparison with the exact results available for a small four-level system. In this case we also compare with results obtained by using the noncrossing approximation and with the usual spinless model calculation.
The concept of an effective Hamiltonian in Fock space is introduced. It is based on the division of the entire one-particle space into subspaces of ‘‘active’’ and ‘‘inactive’’ orbitals. The effective Fock space Hamiltonian has—for active model states—the same eigenvalues as the full Hamiltonian. The theory outlined in this context differs from that of paper I mainly in a different definition of the ‘‘diagonal part’’ of an operator, and in the fact that the ‘‘quasidegenerate case’’ applies throughout. The separation theorem, and as a consequence the connected diagram theorem, is shown to hold, in a more limited sense though, even for those normalizations where it did not in the context of universal wave and energy operators. Unlike in the theory of the ‘‘universal’’ operators of paper I the Fock space and n-particle Hilbert space approaches with analogous normalizations are no longer equivalent. In particular, the Primas normalization with a fully Lie-algebraic structure does not lead to a connected diagram expansion if it is formulated in n-particle Hilbert space, only so in a Fock space formulation. In n-particle Hilbert space with the present definition of the diagonal part of an operator the normalizations b (‘‘canonical’’) and c (‘‘Primas’’) happen to agree. As an alternative to the construction of the wave and energy operator W and L by perturbation theory the nonperturbative approach is presented as a generalization of the coupled-cluster method, in detail both in the intermediate and in the unitary normalization. In the unitary variant only a linear system for σ (the logarithm of the wave operator) has to be solved in order to get L correct through fifth order in perturbation theory with important contributions of higher orders included. A generalization of the Hartree–Fock method to Fock space theory is outlined, which guarantees stationarity of all (active) eigenstates with respect to one-particle transformations. A generalized electron pair theory is also defined. An analysis of the necessary computational steps shows that the nonperturbative approaches do not require significantly more computational effort than perturbation theory to the corresponding order. As a numerical example the H2 molecule in a small basis is discussed.
In a single-j shell the author considers fermion pair and multipole operators coupled to zero angular momentum. The commutation relations of these operators can be satisfied up to first-order corrections by suitably defined q-bosons, onto which the fermion pair operators are mapped. After performing the same mapping to a simple pairing Hamiltonian, it is proved that the pairing energies are also correctly reproduced up to the same order. The small parameter used (T=In Q) is found to be inversely proportional to the size of the shell.