Sets of orbitals are considered, in each of which all the orbitals correspond either individually or pairwise to a single density. We address the questions of whether such orbitals can themselves be a set of solutions of a single, one-particle Schrödinger equation, or whether they can be linearly equivalent to such a set. This is possible for one or two particles, but not in general for more than two particles. Equations relating density, phase and potential in the two-particle case are obtained and discussed. The special form in which the phase is an integral of the density is not in general possible, but a particular density in one dimension for which such is the case is presented. We conclude that equidensity orbitals are rarely of physical significance.
A method is presented for relating a ground-state density distribution to the effective single-particle potential which has this density for its ground state for a noninteracting system of particles. The method is useful for systems consisting of a small number of spinless fermions and in the case of two particles a second-order, nonlinear differential equation relates the density and the effective potential. The question of
v representability is addressed through examples of densities for one- and three-dimensional systems. It is found that densities of the form ${e}^{\ensuremath{-}ar}$ for two-particle systems are not ground-state
v representable. The added flexibility of three dimensions over one allows an effective potential which does not necessarily have the chosen density as its ground state, but as its lowest nondegenerate state.
A new approach for the calculation of ground states of many-electron systems is proposed via an integral formulation of the Hohenberg-Kohn-Sham density-functional theory. Only equations for the total electron density are involved; orbitals are not employed. Exchange and correlation effects are incorporated. In place of the set of single-electron equations, the total electron density is explicitly expressed in terms of the Kohn-Sham effective local potential through multidimensional integrations. The development is based on the first-order density matrix as obtained from the one-body Green's function in polygonal and Fourier path-integral representations. This might open up the possibility of ab initio calculations for molecules with very many electrons. It also provides explicit solutions to two long-standing problems: electron kinetic energy and momentum density as functionals of the total electron density. The formulation can also be used in calculations for general fermions.
In order to calculate the average value of a physical quantity containing also many-particle interactions in a system of
N antisymmetric particles, a set of generalized density matrices are defined. In order to permit the investigation of the same physical situation in two complementary spaces, the Hermitean density matrix of order
k has two sets of indices of each
k variables, and it is further antisymmetric in each set of these indices.Every normalizable antisymmetric wave function may be expanded in a series of determinants of order
N over all ordered configurations formed from a basic complete set of one-particle functions ${\ensuremath{\psi}}_{k}$, which gives a representation of the wave function and its density matrices also in the discrete
k-space. The coefficients in an expansion of an eigenfunction to a particular operator may be determined by the variation principle, leading to the ordinary secular equation of the method of configurational interaction. It is shown that the first-order density matrix may be brought to diagonal form, which defines the "natural spin-orbitals" associated with the system. The situation is then partly characterized by the corresponding occupation numbers, which are shown to lie between 0 and 1 and to assume the value 1, only if the corresponding spin-orbital occurs in all configurations necessary for describing the situation. If the system has exactly
N spin-orbitals which are fully occupied, the total wave function may be reduced to a single Slater determinant. However, due to the mutual interaction between the particles, this limiting case is never physically realized, but the introduction of natural spin-orbitals leads then instead to a configurational expansion of most rapid convergence.In case the basic set is of finite order
M, the best choice of this set is determined by a form of extended Hartree-Fock equations. It is shown that, in this case, the natural spin-orbitals approximately fulfill some equations previously proposed by Slater.
We show that the algebraic quantization method of Heisenberg and the analytical method of Schrödinger are not necessarily equivalent when applied to systems of identical particles. Heisenberg quantization is a natural approach, but inherently more ambiguous and difficult than Schrödinger quantization. We apply the Heisenberg method to the examples of two identical particles in one and two dimensions, and relate the results to the so-called fractional statistics known from Schrödinger quantization. For two particles in d dimensions we look for linear, Hermitian representations of the symplectic Lie algebra sp(d, R). The boson and fermion representations are special cases, but there exist other representations. In one dimension there is a continuous interpolation between boson and fermion systems, different from the interpolation found in Schrödinger quantization. In two dimensions we find representations that can be realized in terms of multicomponent wave functions on a three-dimensional space, but we have no clear physical interpretation of these representations, which include extra degrees of freedom compared to the classical system.
Based on the Schrodinger equation, exact expressions for the non-relativistic particle energy in the local external field and the external field potential are derived as inhomogeneous density functionals. On this basis, it is shown that, when considering more than two noninteracting electrons, the energy of such a system cannot be an inhomogeneous density functional. The result is extended for the system of interacting electrons. This means that the Hohenberg-Kohn lemma which assert that in the ground state to each inhomogeneous density corresponds only one potential of the external field cannot be a justification of the existence of the universal density functional in the general case. At the same time, statements of the density functional theory remain valid when considering any number of noninteracting ground-state bosons due to the Bose condensation effect.