Reduced matrix elements of a tensorial product of n tensor operators in the basis of N-particle angular-momentum eigenstates are expanded into a sum of products of n 1-particle reduced matrix elements and a single (N + n)-particle recoupling coefficient. Application of the formula is illustrated by specific examples. The method leaves the coupling schemes of N-particle states undisturbed, which allows summation over intermediate states in a product of matrix elements to be made for any number of factors. A formula is given for the sum of products of two matrix elements and the extension to a greater number of matrix elements is illustrated by an example which is reduced to a form suitable for numerical evaluation. Such summations over products of matrix elements occur in the perturbation theory of configuration interaction and have hitherto been discussed in terms of effective operators. The connection of the method used here with the effective-operator approach is demonstrated.Reduced matrix elements of a tensorial product of n tensor operators in the basis of N-particle angular-momentum eigenstates are expanded into a sum of products of n 1-particle reduced matrix elements and a single (N + n)-particle recoupling coefficient. Application of the formula is illustrated by specific examples. The method leaves the coupling schemes of N-particle states undisturbed, which allows summation over intermediate states in a product of matrix elements to be made for any number of factors. A formula is given for the sum of products of two matrix elements and the extension to a greater number of matrix elements is illustrated by an example which is reduced to a form suitable for numerical evaluation. Such summations over products of matrix elements occur in the perturbation theory of configuration interaction and have hitherto been discussed in terms of effective operators. The connection of the method used here with the effective-operator approach is demonstrated.

Journal of Mathematical PhysicsApr 1, 19704 citations

The Representation of Single Particle Operators in Two-Particle Form

Eugene Feenberg

Physical ReviewNov 1, 19461 citation

Summation Convention and the Density Matrix in Quantum Theory

BRIAN H. CHIRGWIN

Projection operators may be used instead of vectors to represent the states of a quantum-mechanical system and the appropriate equation of motion is obtained. When a basis is used the basic vectors may be oblique or orthogonal. A formulation appropriate to an oblique basis is developed with the help of tensor methods and the summation convention. This is generalized to be applicable to systems containing $N$ electrons subject to Pauli's exclusion principle. The projection operator corresponding to an arbitrary state is the density operator and is represented by an $N\mathrm{th}$ -order tensor. The well-known tensor operation of contraction of indices applied to the density operator furnishes similar, reduced operators giving one-, two-, or more-particle properties of the system. The one-particle properties are of special interest in chemical systems, the corresponding reduced density matrix being called the charge and bond order matrix by L\"owdin. The full formulas for the reduction of the general density matrix are given, showing the origin of the Coulomb and exchange operators.When the symbolic equation of motion is expressed by means of components and the process of contraction (reduction) is applied, the equation of motion of the one-particle reduction is obtained as well as an expression for the energy of the system. In the special case of the Hartree-Fock approximation the time-dependent wave equations for the one-particle orbitals are shown to satisfy the general equation of motion, suggesting that the energies of the individual orbitals need not be stationary. This approximation is characterized by the idempotent property of the one-particle reduced density matrix. This condition alone leads to a close restriction on the possible values of the charge and bond orders of a molecule. Specific formulas for the molecule butadiene show that these can be expressed in terms of two parameters only, in this case.Projection operators may be used instead of vectors to represent the states of a quantum-mechanical system and the appropriate equation of motion is obtained. When a basis is used the basic vectors may be oblique or orthogonal. A formulation appropriate to an oblique basis is developed with the help of tensor methods and the summation convention. This is generalized to be applicable to systems containing $N$ electrons subject to Pauli's exclusion principle. The projection operator corresponding to an arbitrary state is the density operator and is represented by an $N\mathrm{th}$-order tensor. The well-known tensor operation of contraction of indices applied to the density operator furnishes similar, reduced operators giving one-, two-, or more-particle properties of the system. The one-particle properties are of special interest in chemical systems, the corresponding reduced density matrix being called the charge and bond order matrix by L\"owdin. The full formulas for the reduction of the general density matrix are given, showing the origin of the Coulomb and exchange operators.When the symbolic equation of motion is expressed by means of components and the process of contraction (reduction) is applied, the equation of motion of the one-particle reduction is obtained as well as an expression for the energy of the system. In the special case of the Hartree-Fock approximation the time-dependent wave equations for the one-particle orbitals are shown to satisfy the general equation of motion, suggesting that the energies of the individual orbitals need not be stationary. This approximation is characterized by the idempotent property of the one-particle reduced density matrix. This condition alone leads to a close restriction on the possible values of the charge and bond orders of a molecule. Specific formulas for the molecule butadiene show that these can be expressed in terms of two parameters only, in this case.

Physical ReviewAug 15, 195730 citations

N

electrons subject to Pauli's exclusion principle. The projection operator corresponding to an arbitrary state is the density operator and is represented by an

N\mathrm{th}

-order tensor. The well-known tensor operation of contraction of indices applied to the density operator furnishes similar, reduced operators giving one-, two-, or more-particle properties of the system. The one-particle properties are of special interest in chemical systems, the corresponding reduced density matrix being called the charge and bond order matrix by L\"owdin. The full formulas for the reduction of the general density matrix are given, showing the origin of the Coulomb and exchange operators.When the symbolic equation of motion is expressed by means of components and the process of contraction (reduction) is applied, the equation of motion of the one-particle reduction is obtained as well as an expression for the energy of the system. In the special case of the Hartree-Fock approximation the time-dependent wave equations for the one-particle orbitals are shown to satisfy the general equation of motion, suggesting that the energies of the individual orbitals need not be stationary. This approximation is characterized by the idempotent property of the one-particle reduced density matrix. This condition alone leads to a close restriction on the possible values of the charge and bond orders of a molecule. Specific formulas for the molecule butadiene show that these can be expressed in terms of two parameters only, in this case.