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.
The Hilbert space for three fermions in six orbitals, lately dubbed the "Borland-Dennis setting," is a proving ground for insights into electronic structure. Borland and Dennis discovered that, when referred to coordinate systems defined in terms of its natural orbitals, a wave function in the Borland-Dennis setting has the same structure as a 3-qubit state. By dint of the Borland-Dennis Theorem, canonical forms for 3-qubit states have analogs in the Borland-Dennis setting. One of these canonical forms is based upon "max-overlap Slater determinant approximations." Any max-overlap Slater determinant approximation of a given wave function is the leading term in a 5-term configuration interaction (CI) expansion of that wave function. Our main result is that "max-overlap CIS approximations" also lead to 5-term CI expansions, distinct from those based on max-overlap Slater determinant approximations, though of the same symmetric shape. We also prove the analog of this result for 3-qubit setting.
Slater determinants are product states of filled quantum fermionic orbitals. When they are expressed in a configuration space basis chosen a priori, their entanglement is bound and controlled. This suggests that an exact representation of Slater determinants as finitely-correlated states is possible. In this paper we analyze this issue and provide an exact Matrix Product representation for Slater determinant states. We also argue possible meaningful extensions that embed more complex configuration interaction states into the description.
Since Kato proved his singularity condition for Coulomb potentials in 1957, there has been interest in the creation of wave functions that meet the prescriptions of the cusp conditions, necessary for high-precision quantum-mechanical calculations. It is well known, that wave-function expansions based on Slater determinants of one-electron functions are poorly convergent with respect to satisfying the electron-electron cusp condition. In this contribution we show that with the wavelet expansion of density operators even the local form of the electron-electron cusp condition is easily representable by Slater determinants of one-electron wavelet functions with a proper asymptotics of the expansion coefficients, which is explicitly calculated for Haar wavelets.
Variational quantum Monte Carlo (VMC) method applied to interacting electron systems has played a pivotal role for the studies of electronic states of atoms, molecules and condensed matters. First, the many-body wave functions optimized by the VMC method provide good guiding functions in more accurate, diffusion quantum Monte Carlo (DMC) calculations for identical systems. Second, the VMC calculations themselves can give a good upper bound for the exact ground-state energy of many-electron systems when an appropriate form for the variational wave function is employed. In addition to a conventional form for the variational wave function that is expressed by the product of the Jastrow factor and the single Slater determinant, recent investigations have found that the expression in terms of many Slater determinants can provide a very accurate description of electronic states, especially for intrinsically multi-reference systems, which corresponds to the configuration interaction (CI) expansion method in conventional quantum chemistry. Although the CI method needs an extremely large number of expansion coefficients as variational parameters, the number of parameters can be reduced efficiently by using an idea of (molecular) orbital pair correlations. The purpose of the present paper is to examine the feasibility and usefulness of this idea within the framework of VMC method with the Jastrow–Slater wave function, where the ground state of a water molecule is investigated as a test case. In this study we rely on a variational wave function composed of a product of the Jastrow and Slater parts as 1⁄4 J S; ð1Þ