Abstract The molecular N‐electron problem is formulated in terms of the particle density 𝔔(r) = ∑σ(r − qn) and its canonically conjugated field. Weyl's representation of the canonical commutation relations is used and a characteristic functional of the molecular system is introduced as the expectation value of Weyl's functional exp {i(α, Q) + i(β, P)}. The Hamiltonian equation of motion for the characteristic functional is derived and its cumulant approximation is discussed. The first paper is restricted to a general discussion, independent of a special choice of the Hamiltonian. The density functional representation may be considered as a step towards a formulation of a renormalized quantum chemistry. The lowest order cumulants of the characteristic functional are accessible to actual precision measurements; on the other hand, most experiments are correctly represented by a characteristic functional of the Gaussian type. The significance of the higher order correlations is neither theoretically nor experimentally disclosed yet, their possible importance for biological systems is mentioned, and the question is raised of how far quantum mechanics is empirically confirmed for extremely complex systems.
Abstract The molecular N‐electron problem is formulated in terms of the particle density 𝔔(r) = ∑σ(r − qn) and its canonically conjugated field. Weyl's representation of the canonical commutation relations is used and a characteristic functional of the molecular system is introduced as the expectation value of Weyl's functional exp {i(α, Q) + i(β, P)}. The Hamiltonian equation of motion for the characteristic functional is derived and its cumulant approximation is discussed. The first paper is restricted to a general discussion, independent of a special choice of the Hamiltonian. The density functional representation may be considered as a step towards a formulation of a renormalized quantum chemistry. The lowest order cumulants of the characteristic functional are accessible to actual precision measurements; on the other hand, most experiments are correctly represented by a characteristic functional of the Gaussian type. The significance of the higher order correlations is neither theoretically nor experimentally disclosed yet, their possible importance for biological systems is mentioned, and the question is raised of how far quantum mechanics is empirically confirmed for extremely complex systems.
Abstract A mathematically rigorous reformulation of molecular quantum mechanics in terms of the particle density operator and a canonically conjugated phase field is given. Using a momentum cutoff, it is shown that the usual molecular Hamiltonian can be expressed in terms of the particle density operator and a rigorously defined phase operator. It is shown that this Hamiltonian converges strongly to the cutoff‐free Hamiltonian. In spite of the fact that this Hamiltonian is of second order in the phase operators, all hitherto published expressions are not correct. Unfortunately, the correct formulation destroys the intuitive appeal of using the particle density operator as a coordinate for the many‐body problems of quantum chemistry. Unless somebody provides an essential new and clever idea, we propose to resist the fascination of a local quantum field theory of molecular matter in terms of the particle density operator.
Abstract Density functional theory (DFT) is usually formulated in terms of the electron density as a function of position n(r). Here we discuss an alternative formulation of DFT in terms of the orbital occupation numbers {n α } associated with a local-orbital orthonormal basis set {ϕ α }. First, we discuss how the building blocks of DFT, namely the Hohenberg–Kohn theorems, the Levy–Lieb approach and the Kohn–Sham method, can be adapted for a description in terms of {n α }. In particular, the total energy is now a function of {n α }, E[{n α }], and a Kohn–Sham-like Hamiltonian is derived introducing the effects of the electron–electron interactions via effective potentials, { V α eff = ∂ E e e [ { n β } ] / ∂ n α } . In a second step we consider the Hartree and exchange energies and discuss how to describe them, in the spirit of a DFT approach, in terms of the orbital occupation numbers. In this contribution special attention is paid to the description of the (intra-atomic) correlation energy and corresponding correlation potentials {V corr,α }. For this purpose, a model system is analyzed in detail, whereby an atomic Hamiltonian interacts with the environment via a simplified model; the use of this model allows us to obtain the correlation energy and potentials (in terms of {n α }) for different cases corresponding to low, intermediate and high electron correlations.
We discuss the Legendre conjugate of the Hohenberg-Kohn energy-density functional, i.e., the total energy of an inhomogeneous many-electron system, considered as a functional of the external Coulomb potential (the nuclear Coulomb skeleton of a molecule, for instance) as the starting point of an alternative formulation of a theory of electronic correlations. We then relate this functional to the nonrelativistic or relativistic microscopic many-body theory. The essential bridge between the two theories is many-body perturbation theory perturbing around a mean field. We then point out that a particular choice for the latter, the g-Hartree mean field, leads to a transparent physical picture: The relevant functional of the external field, g0-1, representing electronic correlations, is interpreted as a polarization charge density induced by the latter. This picture, in turn, leads to a Clausius-Mosotti type of equation for this correlation functional. Applications to atomic- and molecular-structure calculations are discussed.
The density matrix for a many-electron system has been examined. A formalism has been arrived at which facilitates its evaluation in terms of a basis corresponding to a discrete spectrum of eigenvalues. This allows a representation to be employed associated with a suitably chosen approximation to the Hamiltonian. Thereby, reasonably accurate estimates of the properties of many-electron systems may be anticipated for low orders of approximation.In developing the formalism, attention was focused upon a means for approximating the quantity exp(zH), where H is the many-particle Hamiltonian and z is a complex number. It was found possible to represent this quantity exactly as an infinite product of exponential factors, each of which depends upon a portion of the Hamiltonian alone. The relation of this result to statistical mechanical applications is indicated. An approximation procedure is described in terms of which various finite products of exponential factors approach the desired quantity in the limit of indefinitely increasing numbers of factors; this limit is approached in a manner that permits any given approximation to contain all the terms of the previous approximation.The first order of approximation was employed to approximate the many-particle density matrix. The resulting theory was applied to the helium-like systems: He, Li+, Be++. The energies of the ground 1S state of helium and the three lowest states of Li+ and Be++ were calculated. The agreement with experimental term values is reasonably satisfactory, the discrepancy between calculations and experiments not exceeding one percent. The triplet-singlet splitting for Li+ was in the order observed; the magnitude calculated was about one-half that observed.The relation between the present theory and the Thomas-Fermi theory is discussed. It is pointed out that the former is the analog of the latter when the density matrix is expressed in other than eigenfunctions of momentum. The quasi-classical character of the approximation is discussed.
Abstract The present day quantum chemistry is mathematically based on von NEUMANN'S formulation of quantum mechanics and therefore not able to deal correctly with anomal quantum states. A general theory of large molecules and large molecular systems has to be founded on quantum field theory allowing for inequivalent irreducible representations. It is proposed to formulate quantum chemistry in the framework of the B*‐algebra of the observables. The paradox of molecular systems having an infinite number of degrees of freedom is discussed, and the possible significance of anomal molecular quantum states for molecular biology is pointed out.