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Physical Review A

Three-dimensional statistical reduction of the N -body Schrödinger equation for electrons with pairwise Coulomb interactions

Boyan Obreshkov

Published Sep 3, 2008• 0 citations
Publisher

Abstract

Based on a second-quantized representation of the nonrelativistic Hamiltonian of a system of $N$ electrons with pairwise Coulomb interactions, we demonstrate the exact statistical reduction of the $N$-body problem to a three-dimensional Schr\"odinger equation for the motion of a single active electron with all other $N\ensuremath{-}1$ electrons acting as spectators. As a by-product, three-dimensional Schr\"odinger equations for the ground and excited states of two-electron atoms and ions are derived and the dynamical role of Pauli's exclusion principle is established. The classical limit $\ensuremath{\hbar}\ensuremath{\rightarrow}0$ of the quantal all-electron equations is examined, and the Thomas-Fermi equation including the Amaldi correction is obtained.

DOI
10.1103/physreva.78.032503

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Based on a second-quantized representation of the nonrelativistic Hamiltonian of a system of NNN electrons with pairwise Coulomb interactions, we demonstrate the exact statistical reduction of the NNN-body problem to a three-dimensional Schr"odinger equation for the motion of a single active electron with all other N\ensuremath−1N\ensuremath{-}1N\ensuremath−1 electrons acting as spectators. As a by-product, three-dimensional Schr"odinger equations for the ground and excited states of two-electron atoms and ions are derived and the dynamical role of Pauli's exclusion principle is established. The classical limit \ensuremathℏ\ensuremath→0\ensuremath{\hbar}\ensuremath{\rightarrow}0\ensuremathℏ\ensuremath→0 of the quantal all-electron equations is examined, and the Thomas-Fermi equation including the Amaldi correction is obtained.
In the framework of recently developed description of the non-relativistic constrained quantum mechanics of systems of NNN-Coulombically interacting electrons [Phys. Rev. {\bf A} 78, 032503 (2008)], we study the relation between spin and statistics in two-electron systems. We find that that the Fermi-Dirac statistics implies lowering of the spatial SO(3) symmetry of the wave-functions of electronic states to Abelian SO(2) rotational subgroup, which is accompanied by reduction of the number of spatial degrees-of-freedom from 6 to 5. We find that the relation between spin and statistics is necessarily related to the anti-symmetry of the relative phase of the spatial part of the two-electron wave-function. We find that it leads to distinct classification of the electronic states according to their relative orbital parity (−1)m(-1)^m(−1)m and total spin S={0,1}S=\{0,1\}S={0,1}. We also find that the Pauli exclusion principle is realized dynamically due to Coulombic interaction between the particles. We find that the broken rotation symmetry of the wave-functions of the electronic states can be restored dynamically, due to conservation of the Laplace-Runge-Lenz vector. We demonstrate that the proposed theoretical description is internally consistent and predictive, and we find the non-equivalence of the above mention representation to the conventional Schr\{o}dinger picture for the description of the quantum dynamics in Coulombic systems with more than one electron.
By means of a quantum mechanical phase space distribution function introduced by von Roos, the Schroedinger equation for a non-relativistic system of N identical particles with scalar interactions is transformed into a quantum mechanical generalization of the Liouville equation, thereby formulating the problem in terms of a generalized density in phase space, a quantity of primary interest in most treatments of the corresponding classical system (or plasma). This transformation permits a parallel development of the theories of classical and quantum plasmas and thus allows the quantum many-body problem to be discussed virtually completely in classical terms. In particular, a kinetic theory of quantum plasmas is obtained by deriving the quantum analogue of the BBGKY hierarchy, and applying thereto approximation techniques similar to those of Rostocker and Rosenbluth, and Bogoliubov. The point of departure from similar previous studies based on the Wigner distribution function is that the proper exchange symmetry can be tractably introduced into the formalism. Attention is first focused on the Hartree and Hartree-Fock approximations, in which case the quantum BBGKY system reduces to a simple quantum generalization of the Vlasov equation. This equation is used to study the response of spatially homogeneous systems to weak external forces, and the associated problems of plasmon and spin-wave excitations. It is also used to derive the quantum and exchange corrected equations of inviscid hydrodynamical transport which are then applied to the problem of sound propagation in the degenerate electron gas. The second part of the study is concerned with the theory of the many-electron atom in the Hartree and Hartree-Fock approximations. The relevant quantum Vlasov equations lead naturally to a statistical theory of the atom which reduces to the Thomas-Fermi-Amaldi and Thomas Fermi models (respectively) as ħ → 0. For ħ ≠ 0, the quantum and exchange corrections to these models are simultaneously generated. The quantum hydrodynamical theory developed earlier is used to determine the influence of these corrections on the boundary conditions of the model, and a theory of the compressed atom is consequently obtained. Considered in somewhat less detail are the effects of non-zero temperature, net orbital angular momentum, relativity and correlations, as well as time dependent processes. The final part deals with the problem of the degenerate electron gas with a uniform neutralizing background. Going beyond the Hartree-Fock approximation, the pair functions for particles with parallel and anti-parallel spin are obtained by neglecting three particle correlations. From these functions, a quantum-mechanical collision integral is derived which differs from that obtained by Silin and Guernsey and conjectured by Wyld and Pines in that dynamical exchange effects are included. Also obtained from the pair function is an expression for the correlation which reduces in the high density limit to the result of Gell-Mann and Brueckner. At intermediate densities an additional term appears in the energy due to the screening of the exchange interaction by the dielectric properties of the medium. It is evaluated in the high density limit and found to be -0.151 r_s ln r_s Ryd/electron in marked disagreement with the corresponding value obtained by DuBois.
The Hamiltonian for an arbitrary Coulomb three-body system is written in closed form in terms of nine generators of three independent o(2,1) algebras and its six physical parameters (i.e., three masses and three charges). Moreover, it is shown that such a Hamiltonian can also be written in the second quantized form by using six pairs of creation and annihilation (boson) operators. The obtained finite-term representation of the Coulomb three-body Hamiltonian in the second quantized form is exact, i.e., it is not based on any approximation. In particular, this means that the original Coulomb three-body problem can be reduced to the equivalent problem of three interacting, complex (i.e., charged) boson fields. The developed procedure opens new avenues in obtaining analytical and semianalytical (or highly accurate) solutions for various Coulomb three-body problems.
A previous derivation of the single-particle Schrödinger equation from statistical assumptions is generalized to an arbitrary number NNN of particles moving in three-dimensional space. Spin and gauge fields are also taken into account. It is found that the same statistical assumptions that imply Schrödinger's equation determine also the form of the gauge coupling terms, and the form of the corresponding local (Lorentz) forces. An explanation for the role of the electrodynamic potentials, as statistical representatives of the Lorentz force, is given. For a single particle, spin one-half is introduced as the property of a statistical ensemble to respond to an external gauge field in two different ways. A generalized calculation, using the twofold number of variables, leads to Pauli's equation. The new spin term is again the statistical representative of the corresponding local force. For a NNN-particle system, spin is introduced as a consequence of gauge coupling.The classical limit ℏ→0\hbar \to 0ℏ→0 of Schrödinger's equation and closely related questions of interpretation of the quantum mechanical formalism are discussed.