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International Journal of Quantum Chemistry

A spin‐dependent unitary group approach to many‐electron systems

M. D. Gould, Graham S. Chandler

Published Oct 1, 1984• 38 citations
Publisher

Abstract

Abstract In this article we derive a segment‐level formula for the matrix elements of the U(2n) generators in a basis symmetry adapted to the subgroup U(n) × U(2) (i.e., spin‐orbit basis), for the representations appropriate to many‐electron systems. This enables the direct evaluation of the matrix elements of spin‐dependent Hamiltonians.

DOI
10.1002/qua.560260403

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Physical Review A•Dec 1, 1980•49 citations
Abstract In this article we derive a segment‐level formula for the matrix elements of the U(2n) generators in a basis symmetry adapted to the subgroup U(n) × U(2) (i.e., spin‐orbit basis), for the representations appropriate to many‐electron systems. This enables the direct evaluation of the matrix elements of spin‐dependent Hamiltonians.
A new spin-dependent unitary group approach to the many-electron correlation problem is investigated. It is demonstrated that the matrix elements of the U(2n) generators, in the U(n)×U(2) adapted electronic Gel’fand basis, are determined by the matrix elements of a single U(n) adjoint tensor operator, herein denoted by Δij(1≤i, j≤n), where Δ is a polynomial of degree two in the U(n) matrix E=[Eij]. The method is then applied, in the second paper of the series, to derive a simple segment level formula for the matrix elements of all U(2n) generators. The advantages of this new procedure for computer implementation are discussed and the central role played by the matrix Δ for the determination of molecular spin densities is highlighted.
A fully spin-adapted approach to many-electron density matrices is developed in the context of the unitary group approach to many-electron systems. An explicit expression for the single-electron spin-density operator, as a polynomial of degree two in the orbital U(n) generators, is derived for the case of spin-independent systems. Extensions to spin-dependent systems are also considered, leading to the appearance of total-spin transition densities, whose general properties are investigated. A corresponding formalism for the two-electron density matrix, which is capable of further generalization, is also developed. The results of this paper, together with recent developments on the matrix elements of the U(2n) generators in the electronic Gel’fand basis, afford a versatile method for the direct calculation of one- and two-body density matrices in the unitary group approach framework.
Abstract The fermion unitary group formulation (UGF) of many‐body theory is based on the unitary group U(2n) where n is the number of freeon orbitals. This formulation, which conserves particle‐number but not spin, is isomorphic to the particle‐number‐conserving, second‐quantized formulation (SQF). In UGF we derive the familiar diagrammatic algorithm for matrix elements, M(Y) = (−1)H+L where H and L denote the numbers of hole lines and loops in the diagram D(Y) of M(Y). The unitary group derivation is considerably simpler than is the conventional, second‐quantized derivation that employs time‐dependence, Wick's theorem, normal‐order, and contractions. In neither fermion UGF nor SQF is spin conserved. We carry out in UGF the spin‐projection (symmetry adaptation to SU(2)) of the fermion vectors and obtain with a spin‐free Hamiltonian the same matrix elements as with the freeon UGF (part 24 of this series). The fermion unitary group formulation for a spin‐free Hamiltonian should be regarded as an alternate path to spin‐free quantum chemistry.
Abstract The representation of an N‐electron Schrödinger Hamiltonian on an orthonormal, spin‐free (freon) orbital product space is exactly modeled by a second‐degree polynomial in the infinitesimal generators of the unitary group. Symmetry adaptation of the orbital product space with respect to the symmetric group yields Gel'fand states which provide base for irreducible represntations of the unitary group. These exist in closed form as, in consequence, does the representation of the model Hamiltonian in this same basis. We retain as physical only those states characterized by tableaux with no more than two columns for which the spin labelling is one‐half the difference in the lengths of the two columns. The unitary group formulation is equivalent to standard, number‐conserving, second‐quantized, many‐body theory.
Graphical methods of spin algebras are used to derive the expressions for the matrix elements of the total particle-number-conserving operators in the basis of hole-particle states, adapted to the chain $\mathrm{U}({n}^{\ensuremath{'}}+{n}^{\ensuremath{'}\ensuremath{'}})\ensuremath{\supset}\mathrm{U}({n}^{\ensuremath{'}})\ensuremath{\bigotimes}\mathrm{U}({n}^{\ensuremath{'}\ensuremath{'}})$, where ${n}^{\ensuremath{'}}$ and ${n}^{\ensuremath{'}\ensuremath{'}}$ designate dimensions of particle and hole subspaces, respectively. The matrix elements are expressed as a product of segment values, each associated with one orbital level as in the particle formalism, and of an additional segment value, representing a linkage of the hole and particle subspaces. It is shown that the particle formalism segment values can be used throughout except for the link segment, whose possible values are derived. An example of hole-particle bases and of their graphical representations is given and the advantages of the hole-particle formalism in shell-model calculations are outlined. An extension of this formalism to particle-number-nonconserving operators, needed in applications involving the $m\mathrm{p}\ensuremath{-}n\mathrm{h}$ propagators with $m\ensuremath{\ne}n$, mmm, n=0n=0n=0, 1, and 2, is discussed.