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Physical Review A

Variational equation of states of arbitrary angular momentum for two-particle systems

Tapan K. Mukherjee, Prasanta Kumar Mukherjee

Published Jul 1, 1994• 31 citations
Publisher

Abstract

Work on the reduction of independent variables in the Schr\"odinger equation for two-particle systems from six to three is extended to give a closed expression of the variational equation for states of arbitrary total angular momentum. The method consists of writing the Hamiltonian in six coordinates, by a suitable choice of transformation equations, and evaluating integrals involving real angular-momentum functions. An existing variational equation for P states follows as a special case of the present formalism.

DOI
10.1103/physreva.50.850

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Work on the reduction of independent variables in the Schr"odinger equation for two-particle systems from six to three is extended to give a closed expression of the variational equation for states of arbitrary total angular momentum. The method consists of writing the Hamiltonian in six coordinates, by a suitable choice of transformation equations, and evaluating integrals involving real angular-momentum functions. An existing variational equation for P states follows as a special case of the present formalism.
In quantum mechanics, as well as in classical mechanics, the number of variables involved in the equations of motion may be reduced by utilizing the constants of motion of the system. For a set of N particles moving in a field-free space there are six integrals if N is greater than two. These correspond to the laws of conservation of linear and of angular momentum. It is the purpose of this paper to eliminate the coordinates of rotation and of translation of the total system from the Schrodinger equation and to obtain a new set of differential equations involving only 3N-6 variables.1
The global rotational degrees of freedom in the Schr\"odinger equation for an N-body system are completely separated from the internal ones. After removing the motion of the center of mass, we find a complete set of (2l+1)(2\mathcal{l}+1)(2l+1) independent base functions with angular momentum l.\mathcal{l}.l. These are homogeneous polynomials in the components of the coordinate vectors and the solutions of the Laplace equation, where the Euler angles do not appear explicitly. Any function with given angular momentum and given parity in the system can be expanded with respect to the base functions, where the coefficients are the functions of the internal variables. With the right choice of the base functions and the internal variables, we explicitly establish the equations for those functions. Only $(3N\ensuremath{-}6)$ internal variables are involved both in the functions and in the equations. The permutation symmetry of the wave functions for identical particles is discussed.
Since the conformation of physical systems is often advantageously described with the help of generalized (i.e. curvilinear) coordinates, the following questions are raised and general answers given to them: (i) What are the components of the momentum operators, those of the adjoint momentum operators and those of the hermitian momentum operators? (ii) What is the general form of the hamiltonian operator? (iii) What do the general forms of the momentum and hamiltonian operators become when expressed in terms of quasi-momentum operators (e.g. angular momentum component operators)? (iv) How are the answers to the above questions affected by an arbitrary choice of normalization convention for the total wave-function? A complete set of formulae (whatever the independent choices of coordinates, quasi-momentum operators and normalization) is given and various ‘historical’ formulae are shown to be particular instances of the general formulae proposed.
The configuration-space approach to the three-particle problem is generalized to the case of four particles. Special coordinates are defined which have simple symmetry properties with respect to the exchange of identical particles. The construction of a suitable orthogonal system is discussed. Some of these functions are given explicitly. It is pointed out that the use of this orthogonal system leads to a considerable simplification for a large number of four-particle problems, namely, the approximate reduction of the Schrödinger equation to a finite system of coupled differential equations for functions that depend on one variable only.
The quantum dynamical evolution of atomic and molecular aggregates, from their compact to their fragmented states, is parametrized by a single collective radial parameter. Treating all the remaining particle coordinates in d dimensions democratically, as a set of angles orthogonal to this collective radius or by equivalent variables, bypasses all independent-particle approximations. The invariance of the total kinetic energy under arbitrary d -dimensional transformations which preserve the radial parameter gives rise to novel quantum numbers and ladder operators interconnecting its eigenstates at each value of the radial parameter. We develop the systematics and technology of this approach, introducing the relevant mathematics tutorially, by analogy to the familiar theory of angular momentum in three dimensions. The angular basis functions so obtained are treated in a manifestly coordinate-free manner, thus serving as a flexible generalized basis for carrying out detailed studies of wavefunction evolution in multi-particle systems.
The quantization of orbital angular momentum can be introduced simply through the model of the two- and three-dimensional simple harmonic oscillator. Most of the analysis is carried out in the familiar Cartesian coordinate system in which the simple harmonic oscillator Schrödinger equation is separable. Angular momentum eigenfunctions are constructed by superposition, and the resulting functions easily transformed into spherical coordinates. The angle-dependent parts of the solutions are the spherical harmonics, which are the orbital angular momentum eigenfunctions for all central potentials including the Coulomb potential of the hydrogen atom. The method also introduces the separation of variables technique and provides practice in applying the concepts of completeness, orthogonality, superposition of states, and alternative representations.