Diagrammatic non-degenerate RSPT for evaluation of ground-state energy of simple open-shell molecular systems

The diagrammatic non-degenerate Rayleigh-Schrödinger perturbation theory and the coupled cluster approach are applied to the evaluation of the ground state energy of a simple open-shell molecular system described in the zeroth order approximation by a single determinant wavefunction. The corresponding hamiltonian is built up by the creation and annihilation operators introduced over an orthonormal set of restricted Hartree-Fock one-particle functions. The perturbation H₁ is composed of one- and two-particle terms, the one-particle term depending in an explicit way upon the type of restricted Hartree-Fock theory used. The efficiency of the elaborated theory is illustrated for the BeH molecule.     

Higher-order approximations for the particle-particle propagator

A new type of approximations for many-body Green's functions proposed recently is applied to the particle-particle (pp) propagator for anN-particle fermion system. The new approach which is referred to as the algebraic diagrammatic construction (ADC) is based on an exact resummation of the perturbation series for the pp-propagator in terms of a simple algebraic form introducing energy-independent effective interaction matrix elements and transition amplitudes. These effective quantities are represented by perturbation expansions and can be determined consistently through a given ordern of perturbation theory by comparing the algebraic form with the diagrammatic perturbation series of the pp-propagator through ordern. By this procedure one obtaines a systematic set of approximation schemes (ADC(n)) that represent infinite partial summations for the pp-propagator being complete throughnth order of perturbation theory. The explicit ADC equations forn=1 and 2 are presented and discussed. Comparison is made with the particle-particle random phase approximation (RPA). It is demonstrated that the second-order ADC scheme constitutes an essential step beyond the RPA which is consistent only through first order.     

Calculation of spin-density matrix by diagrammatic perturbation theory

A diagrammatic perturbation-theory method for direct calculation of spin-density matrix of open-shellN-electron systems described by the restricted Hartree-Fock one-particle functions is formulated. The formulae correct up to the second order of perturbation theory (second order in correlation effects) are presented. Their generalization to account for infinite summations of dominant correlation effects is simple, realized by making use of the so-called coupled cluster approach.     

The E.S.R. spectrum of the tropolonyl radical

The many-body diagrammatic Rayleigh-Schrödinger perturbation theory (RSPT) is used for the calculation of ionization potentials of open-shell systems with one unpaired electron. This theoretical approach is tested on the simple examples of NO₂ and NF₂ molecules described by the INDO semi-empirical hamiltonian. The first- and second-order results are presented.     

Direct calculation of ionization energies

The advantages of the propagator formalism, as a direct method of calculating ionization energies, are stressed. The propagator equations are derived for closed-shell systems using an operator method instead of the usual diagrammatic derivations. The equations enable the development of an interpretation of the ionization energies in terms of conceptually simple quantities, such as pair correlation energies and associated relaxation effects, and retain the idea of orbital ionization. Infinite summations appearing in the self-energy terms are replaced by finite expressions involving functions satisfying uncoupled inhomogeneous differential equations. Certain high-order propagator equations are derived, and a connection with the Bethe-Goldstone formulation of pair correlation is made. Several computational procedures are advocated as forming the basis for balanced calculations of atomic and molecular ionization energies.     

On the zero-bandwidth limit in diagrammatic perturbation technique for a model of an intermediate valent impurity

The limit of zero bandwidth in a model for an intermediate valent impurity is studied in direct diagrammatic perturbation technique in terms of the hybridization. The class of diagrams, from which this limit is obtained, is resummed. Furthermore, a Brillouin-Wigner-type expansion is set up.     

Bold diagrammatic Monte Carlo technique: when the sign problem is welcome

We introduce a Monte Carlo scheme for sampling a bold-line diagrammatic series specifying an unknown function in terms of itself. The range of convergence of this bold(-line) diagrammatic Monte Carlo (BMC) technique is significantly broader than that of a simple iterative scheme for solving integral equations. With the BMC technique, a moderate "sign problem" turns out to be an advantage in terms of the convergence of the process. For an illustrative purpose, we solve the one-particle s-scattering problem. As an important application, we obtain the T matrix for a Fermi polaron (one spin-down particle interacting with the spin-up fermionic sea).     

Theory of irreversible processes in nonequilibrium quantum systems. I. General formalism

The theory of Van Hove for nonequilibrium quantum statistical mechanics is extensively reformulated in terms of a superspace (a kind of operator space). This reformulation enables us to introduce a diagrammatic method which makes it convenient to deal with practical problems in physical systems. In our formalism, quantum statistical effects are considered on the basis of a systematic rule for the contraction technique. A complicated statistical effect in boson or fermion systems can be treated by starting with a simple unsymmetrized formalism in the Boltzmann statistics.     

Quantum field methods in the theory of diffusion-controlled reactions

The diagrammatic perturbation technique for the kinetic theory of classical reacting systems with diffusion is developed. It is further applied to investigation of recombination-type reactions in media of one, two, and three dimensions. The effective rates of this reaction are calculated, covering the whole range from the slow to the fast (diffusion-controlled) regimes.     

Many-body diagrammatic treatment of electronicg-tensor

The many-body diagrammatic theory of electronicg-tensor components taking into account also the correlation effects is elaborated. The resulting perturbation expressions are used for calculation ofg-tensor components of some small open shell systems within the INDO semiempirical method.     

Nuclear field theory

By using path integral techniques nuclear field theory (NFT) is developed for Fermi systems interacting via a general two-body force. The NFT Lagrangian is strictly derived. As a by-product, the corresponding graphical rules are obtained. The relation between the NFT and the conventional Feynman diagrammatic many-body perturbation theory is established for processes connecting initial and final states, too.     

Semiclassical approach to orbital magnetism of interacting diffusive quantum systems

We study interaction effects on the orbital magnetism of diffusive mesoscopic quantum systems. By combining many-body perturbation theory with semiclassical techniques, we show that the interaction contribution to the ensemble-averaged quantum thermodynamic potential can be reduced to an essentially classical operator. We compute the magnetic response of disordered rings and dots for diffusive classical dynamics. Our semiclassical approach reproduces the results of previous diagrammatic quantum calculations.     

Many-body diagrammatic expansion in a kohn-sham basis: implications for time-dependent density functional theory of excited states

We formulate diagrammatic rules for many-body perturbation theory which uses Kohn-Sham Green's functions as basic propagators. The diagram technique allows one to study the properties of the dynamic nonlocal exchange-correlation (xc) kernel f(xc). We show that the spatial nonlocality of f(xc) is strongly frequency dependent. In particular, in extended systems the nonlocality range diverges at the excitation energies. This divergency is related to the discontinuity of the xc potential.     

Cumulants in perturbation expansions for non-equilibrium field theory

The formulation of perturbation expansions for a quantum field theory of strongly interacting systems in a general non-equilibrium state is discussed. Non-vanishing initial correlations are included in the formulation of the perturbation expansion in terms of cumulants. The cumulants are shown to be the suitable candidate for summing up the perturbation expansion. Also a linked-cluster theorem for the perturbation series with cumulants is presented. Finally, a generating functional of the perturbation series with initial correlations is studied. We apply the methods to a simple model of a fermion-boson system.     

Functional methods in thermofield dynamics: A real-time perturbation theory for quantum statistical mechanics

A generating functional is constructed for real-time Green functions in quantum statistical mechanics in the context of thermofield dynamics. The KMS condition is taken as an axiom which together with field equations fixes the generating functional for causal Green functions in an interacting quantum field theory. This leads to Feynman rules for diagrammatic real-time perturbation theory.     

On the use of MP2 theory for electron molecules correlation in atoms and molecules

The use of Moeller-Plesset perturbation theory, frequently designated MPn, in describing electron correlation in atomic and molecular systems is critically examined. Some recently published studies have examined the higher terms in the Moeller-Plesset perturbation expansion and the convergence behaviour of the perturbation series. From these investigations conclusions about the applicability of the low order theory have been drawn which, in view of the widespread use of MP2, demand more thorough analysis. Combining the Rayleigh-Schrödinger and the Brillouin-Wigner perturbation expansions avoids an infinite order expansion and yields a closed expression which consists of the MP2 energy components together with a remainder term. The applicablity of MP2 theory then rests upon the magnitude of this remainder term rather than the behaviour of the higher order terms in the perturbation series.     

无限次微扰理论的分块矩阵法证明

无限次微扰理论是求解无序体系格林函数的理论方法。此方法是吴式玉教授及其合作者们用“图式法”获得的。本文采用把矩阵分块,求解子矩阵方程的方法,推导了这一理论的结果,从而给出了这一理论的矩阵代数证明。 关键词：     

Rates of diffusion-limited reaction in periodic systems

The pseudopotential and perturbation theory are used to derive the first three terms in the expansion of the smallest eigenvalue of the Helmholtz equation both for infinite two-dimensional systems with an array of perfectly absorbing circles centered on (1) a square lattice and (2) a triangular lattice, and also for infinite three-dimensional systems both with arrays of perfectly absorbing interspersed cylinders and with an array of perfectly absorbing spheres centered on (1), a simple cubic lattice, (2) a body-centered cubic lattice, and (3) a facecentered cubic lattice. In all cases, the perturbation parameter involves the ratio of the radius of the absorber to the lattice spacing. These eigenvalues and the corresponding eigenfunctions are used to compute the first three terms of expansions of the first passage time of a diffusing point particle randomly placed outside the absorbers. Expressing the perturbation parameter as a function of the area or volume fraction occupied by the absorbers reveals a remarkable similarity among the rates of diffusion-limited reaction for arrays of absorbers and the corresponding radially symmetric system containing one central absorber.     

Effective temperature scattering matrix and kinematic mechanism of cooper instability in antiferromagnetic rare-earth intermetallides

An effective temperature-dependent scattering matrix for a localized subsystem is obtained in the periodic Anderson model by summing itinerant variables in the diagrammatic series of perturbation theory. The effective interaction that occurs in this case can lead to an antiferromagnetic phase, a superconducting phase, and the phase of coexisting superconductivity and antiferromagnetism observed in heavy-fermion intermetallic compounds.