A size-extensive multidimensional many-body theory is developed from an order-expanded van Vleck transformation. This provides an effective Hamiltonian in a model space consisting of a set of determinants whose zeroth-order energies may be nondegenerate. Expressions for the effective Hamiltonian in terms of the perturbation and a set of resolvents generalized from the Rayleigh–Schrödinger form are given. Perturbative evaluation of the resultant formulas via diagrammatic expansion is illustrated and discussed. The diagrams required through second order for a model space consisting of a Hartree–Fock solution plus selected singly and doubly excited determinants are presented, and their relation to those employed in the method of Hose and Kaldor is discussed.
Many-body perturbation theory (MBPT) based on Green’s functions and Feynman diagrams provides a fundamental theoretical framework for various ab initio computational approaches in molecular and materials science, including the random phase approximation (RPA) and GW approximation. Unfortunately, this perturbation expansion often fails in systems with strong multireference characters. Extending diagrammatic MBPT to the multireference case is highly nontrivial and remains largely unexplored, primarily due to the breakdown of Wick’s theorem. In this work, we develop a diagrammatic multireference generalization of MBPT for computing correlation energies of strongly correlated systems, by using the cumulant expansion of many-body Green’s functions in place of Wick’s theorem. This theoretical framework bridges the gap between MBPT in condensed matter physics and multireference perturbation theories (MRPT) in quantum chemistry, which had been almost exclusively formulated within time-independent wave function frameworks prior to this work. Our formulation enables the explicit incorporation of strong correlation effects from the outset as in MRPT, while treating residual weak interactions through a generalized diagrammatic perturbation expansion as in MBPT. As a concrete demonstration, we formulate a multireference (MR) extension of the standard single-reference (SR) RPA by systematically resumming generalized ring diagrams, which naturally leads to a unified set of equations applicable to both SR and MR cases. Benchmark calculations on prototypical molecular systems reveal that MR-RPA successfully resolves the well-known failure of SR-RPA in strongly correlated systems. This theoretical advancement paves the way for advancing ab initio computational methods through diagrammatic resummation techniques in future.
In the conventional perturbation treatment of the many-body problem of interacting particles, the zero-order Hamiltonian corresponds to independent particles moving in a static over-all potential. A discussion of the effects of particle interactions or `correlations' shows that if one starts instead with a Hamiltonian representing noninteracting particles in a velocity-dependent over-all potential, deeper for slow, and shallower for fast particles, then part of the correlation effect is included already in zero order. In addition, a velocity-dependent over-all potential may be called for by velocity dependent interparticle forces or by exchange forces. The degree of the improvement in the convergence of a perturbation expansion based on a Hamiltonian with a velocity-dependent over-all potential is discussed and illustrated by a simple example in which the velocity dependence of the potential gives rise to a reduced "effective mass" of the particles.The many-body problem of a large, uniform system of interacting particles (e.g., the case of a heavy nucleus without surface effects) is formulated in detail in perturbation theory, starting with a velocity-dependent potential constant in space. The work involved in such a calculation turns out to be essentially the same as with a velocity-independent potential, the effect of the velocity dependence being to reduce each term in the perturbation expansion by a constant factor raised to a power equal to the number of "energy denominators" ${E}_{m}\ensuremath{-}{E}_{n}$ in the term in question. A simple equation is deduced for the optimum degree of velocity dependence of the over-all potential which ensures the most rapid convergence.
A comprehensive and detailed account is presented for the finite-temperature many-body perturbation theory for electrons that expands in power series all thermodynamic functions on an equal footing. Algebraic recursions in the style of the Rayleigh-Schrödinger perturbation theory are derived for the grand potential, chemical potential, internal energy, and entropy in the grand canonical ensemble and for the Helmholtz energy, internal energy, and entropy in the canonical ensemble, leading to their sum-over-states analytical formulas at any arbitrary order. For the grand canonical ensemble, these sum-over-states formulas are systematically transformed to sum-over-orbitals reduced analytical formulas by the quantum-field-theoretical techniques of normal-ordered second quantization and Feynman diagrams extended to finite temperature. It is found that the perturbation corrections to energies entering the recursions have to be treated as a nondiagonal matrix, whose off-diagonal elements are generally nonzero within a subspace spanned by degenerate Slater determinants. They give rise to a unique set of linked diagrams-renormalization diagrams-whose resolvent lines are displaced upward, which are distinct from the well-known anomalous diagrams of which one or more resolvent lines are erased. A linked-diagram theorem is introduced that proves the size-consistency of the finite-temperature many-body perturbation theory at any order. General-order algorithms implementing the recursions establish the convergence of the perturbation series toward the finite-temperature full-configuration-interaction limit unless the series diverges. The normal-ordered Hamiltonian at finite temperature sheds light on the relationship between the finite-temperature Hartree-Fock and first-order many-body perturbation theories.
Background There are two stages in the study of perturbation theory and related techniques (although they are mixed intimately in most derivations in the literature). The first is the formal development , carried out in terms of the total Hamiltonian and total wave function (and total zero-order wave function), without attempt to express anything in terms of one- and two-body quantities (components of Ĥ, orbitals, integrals over orbitals etc.). We can make a considerable amount of progress in this way before considering the detailed form of Ĥ. The second is the many-body development , where all expressions are obtained in terms of orbitals (one-electron states) and oneand two-electron integrals. We shall try to keep these separate for a while and begin with a consideration of formal perturbation theory. Another aspect of the study of many-body techniques is the large variety of approaches, notations and derivations that have been used. Each different approach has contributed to the lore and the language of many-body theory, and each tends to illuminate some aspects better than the other approaches. If we want to be able to read the literature in this field, we should be familiar with several alternative formulations. Therefore, we shall occasionally derive some results in more than one way and, in particular, we shall derive the basic perturbation-theory equations and their many-body representations in several complementary ways. Classical derivation of Rayleigh–Schrödinger perturbation theory The perturbation Ansatz We begin with a classical textbook derivation of formal Rayleigh–Schrödinger perturbation theory (RSPT).