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arXiv:1904.06378

On the permutation symmetry of atomic and molecular wavefunctions

Francisco Marcelo Fernández

Published Apr 12, 2019• 0 citations
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Abstract

In this paper we analyze a recently proposed approach for the construction of antisymmetric functions for atomic and molecular systems. It is based on the assumption that the main problems with Hartree-Fock wavefunctions stem from their lack of proper permutation symmetry. This alternative building approach is based on products of a space times a spin function with opposite permutation symmetry. The main argument for devising such factors is that the eigenfunctions of the non-relativistic Hamiltonian are either symmetric or antisymmetric with respect to the transposition of the variables of a pair of electrons. However, since the eigenfunctions of the non-relativistic Hamiltonian are basis for the irreducible representations of the symmetric group they are not necessarily symmetric or antisymmetric, except in the trivial case of two electrons. We carry out a simple and straightforward general analysis of the symmetry of the eigenfunctions of the non-relativistic Hamiltonian and illustrate our conclusions by means of two exactly-solvable models of $N=2$ and $N=3$ identical interacting particles.

DOI
10.48550/arxiv.1904.06378

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In this paper we analyze a recently proposed approach for the construction of antisymmetric functions for atomic and molecular systems. It is based on the assumption that the main problems with Hartree-Fock wavefunctions stem from their lack of proper permutation symmetry. This alternative building approach is based on products of a space times a spin function with opposite permutation symmetry. The main argument for devising such factors is that the eigenfunctions of the non-relativistic Hamiltonian are either symmetric or antisymmetric with respect to the transposition of the variables of a pair of electrons. However, since the eigenfunctions of the non-relativistic Hamiltonian are basis for the irreducible representations of the symmetric group they are not necessarily symmetric or antisymmetric, except in the trivial case of two electrons. We carry out a simple and straightforward general analysis of the symmetry of the eigenfunctions of the non-relativistic Hamiltonian and illustrate our conclusions by means of two exactly-solvable models of N=2N=2N=2 and N=3N=3N=3 identical interacting particles.
Abstract It is well known that the allowed wavefunctions for an N -electron system should be antisymmetric with respect to the permutation of any pair of electron labels. On the other hand, the Hamiltonian for such a system is invariant under any permutation of electron labels and, consequently, its eigenfunctions are the basis for the irreducible representations of the symmetric group S N . Here, we investigate which symmetry species of the S N group are compatible with the antisymmetry principle. We illustrate the conclusions by means of simple N -particle one-dimensional models with harmonic interactions.
It is well known that the allowed wavefunctions for an N-electron system should be antisymmetric with respect to the permutation of any pair of electron labels. On the other hand, the Hamiltonian for such system is invariant under any permutation of electron labels and, consequently, its eigenfunctions are basis for the irreducible representations of the symmetric group SN.Here, we investigate which symmetry species of the SN group are compatible with the antisymmetry principle. We illustrate the conclusions by means of simple N-particle one-dimensional models with harmonic interactions.
A method for the calculation of translationally invariant wave functions for systems of identical fermions with arbitrary potential of pair interaction is developed.It is based on the well-known result that the essential dynamic part of Hamiltonian for the system of identical particles is the reduced Hamiltonian operator describing a relative movement of two particles inside the system.The eigenfunctions of this operator take into account all correlations caused by interaction.These eigenfunctions are basic elements for building the components (i.e., the functions with a lower degree of antisymmetry) used to construct the total antisymmetric wave function of the system.The main problem of this approach appears to be the antisymmetrization of the components.The developed universal algorithm for antisymmetrization gives a possibility to carry out this operation in a simple way and to keep numerical approximations under control.
The symmetry properties of the N-particle multilevel system are studied. For indistinguishable particles, the total wave function must be either symmetric or antisymmetric in the exchange of any two particles. The internal states of the multilevel system are combined with suitable spatial wave functions to produce a totally symmetric or antisymmetric wave function. The problem of degeneracy and the method of combining a given permutational symmetry of the internal wave function with the same or the conjugate symmetry for the spatial part are described. It is found that Young’s diagram corresponding to the given irreducible representation of the permutation group plays an important role.
A system of NNN antisymmetric particles, moving under the influence of a fixed potential and their mutual many-particle interactions, is investigated in the ordinary Hartree-Fock scheme, having the total wave function approximated by a single Slater determinant. It is shown that all the density matrices of various orders, the wave function, and the entire physical situation depends only on a fundamental invariant $\ensuremath{\rho}({x}_{1}, {x}_{2})$, which is identical with the first-order density matrix. The Hartree-Fock equations are expressed in terms of this quantity.The Hartree-Fock equations are also solved by expanding the eigenfunctions in a given complete set, and applications to the MO-LCAO theory of the electronic structure of molecules, and crystals are given. It is shown that, in this scheme, the entire physical situation depends on a charge- and bond-order matrix $R(\ensuremath{\nu}\ensuremath{\mu})$ with respect to the ordinary atomic spin-orbitals involved. The Hartree-Fock equations for this matrix are investigated.Finally, the ionized and excited states are investigated, and it is shown that the Hartree-Fock scheme has a high degree of physical visuality also in case of many-particle interactions. The excitation energy of the system is the difference (${{\ensuremath{\omega}}_{j}}^{\ensuremath{'}}\ensuremath{-}{\ensuremath{\omega}}_{i}$) between two "spin-orbital energies," being eigenvalues to the effective Hamiltonians associated with the two states under consideration.
The symmetrization postulate (SP) states that wave functions are either completely symmetric or completely antisymmetric under permutations of identical particles. It is shown by one-dimensional counter-examples that SP is not demanded by the usual physical interpretation of the mathematical formalism of wave mechanics unless one makes use of further physical properties of real systems; the error in a standard proof of SP which ignores these properties is pointed out. It is then proved that SP is true for those systems of spinless particles which have the following properties: (a) probability densities are permutation-invariant, (b) allowable wave functions are continuous with continuous gradient, (c) the 3n3n3n-dimensional configuration space is connected, (d) the Hamiltonian is symmetric, and (e) the nodes of allowed wave functions have certain properties. The counterexamples show that SP is not a necessary property of those systems which do not have property (c). The proof is extended to particles with internal degrees of freedom (including spin) by noting that any observable commutes with every permutation and making use of a particular observable acting only on internal variables. Extraneous mathematical assumptions, such as that of the existence of a "complete" set of commuting observables, criticized by Messiah and Greenberg, are not employed. Some comments are made on the conventional nature of the concept of identity for similar particles; the equivalence between the usual formulation in which different species of similar particles are treated as distinct, and that in which they are regarded as identical particles in different internal states, is emphasized.