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A NOTE ON THE DYNAMICAL SYMMETRY OF THE HYDROGEN ATOM

Chuan-Jie Zhu

Published Feb 1, 2025• 0 citations
Publisher

Abstract

The quantum mechanics of the hydrogen atom can be solved algebraically by the dynamical symmetry. In this note we introduced firstly Pauli's derivation of the complete relations among the various basic states with the same eigenvalue of the Hamiltonian. Secondly we also derived the same results by using algebraic method and some relations among the associated Legendre functions. As a byproduct, we also obtained a recursive relation of the radial wave functions. By using this recursive relation, we can derive the general radial wave function from the most simple radial wave function which has only an monomial term, much like deriving a general state from the highest weight state by using ladder operators.

DOI
10.26599/phys.2025.9320101

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•Jan 1, 2007•0 citations
The quantum mechanics of the hydrogen atom can be solved algebraically by the dynamical symmetry. In this note we introduced firstly Pauli's derivation of the complete relations among the various basic states with the same eigenvalue of the Hamiltonian. Secondly we also derived the same results by using algebraic method and some relations among the associated Legendre functions. As a byproduct, we also obtained a recursive relation of the radial wave functions. By using this recursive relation, we can derive the general radial wave function from the most simple radial wave function which has only an monomial term, much like deriving a general state from the highest weight state by using ladder operators.
This chapter physical properties of the hydrogen atom and its Hamiltonian function as a particle in a spherically symmetric potential having a wave function as a product of the radial function and spherical harmonic function. Hereafter, it comes to two independent wave equations: the radial equation and the angular equation. After some derivation, it is shown that the angular equation is a product of the azimuthal angle equation and polar angle equation (as discussed in the previous chapter). The azimuthal angle equation is similar to the particle in a ring problem from the previous chapter and after some derivation the polar angle equation becomes an associated Legendre equation with well-known polynomials as solutions. Next, the solution to the radial equation is presented which becomes after some derivation an associated Laguerre equation with well-known polynomials as solutions and from this result is obtained the energy equation for the hydrogen-like atom. Subsequently, it is derived the normalization constant of the radial function. Afterwards, the numerical analysis of the radial equation of the hydrogen atom along with its corresponding Fortran code is presented. Finally, the hydrogen atomic orbitals equations and plots are depicted followed by the fine structure of the hydrogen (198 words).
The radial form of Hylleraas’ equation for the hydrogen atom, Λl‖El〉=4ℏ4a−2‖El〉 (a=Bohr radius), is considered and it is shown that the operator Λl can be factorized. Hence ladder operators P±l are derived that are linear in the position operator r and are nonlinear functions of the momentum operator p. It is proven that P±l‖El〉 =2ℏ2a−1[1+(l+ (1)/(2) ± (1)/(2) )2 ×(2Mℏ−2a2E)]1/2‖E,l±1〉. In the momentum representation of wave mechanics the solutions to these equations are the radial momentum-space wavefunctions for the hydrogen atom. Thus a simple method of calculating these wavefunctions is obtained. The results complement the familiar operator solution for the hydrogen atom that is based on factorization of the radial Hamiltonian and yields operators that are linear in p and are nonlinear functions of r.
By invoking a standard variable transformation x → y ≡ x 2 that connects the eigenvalue problems of the hydrogen atom system (Coulomb potential) and the Kratzer oscillator system , we obtain a system of ladder operators Ω nl ± ( l = 0,1,2, ... , n − 1) that connect the degenerate energy eigenstates (belonging to different l -values) of the hydrogen atom system. Using such quantum number specific operators as the precursors, we develop a general method of constructing quantum number independent ladder operators ; and then investigate the general conditions for these operators to form a realization of the su (2) algebra. In the process, we demonstrate that, in general, a finite-dimensional linear vector space carries a realization of the su (2) algebra. Applying the method to the case at hand, we show that for the hydrogen atom system the operators and form an su (2) algebra. The Hamiltonian is identified with the Casimir operator of the algebra, thereby revealing a dynamical SU (2) group symmetry of the hydrogen atom system.
This chapter begins with the simple solution of the Schrödinger equation for hydrogen atom for which the energy value has been derived. The Bohr radius of H atom has also been computed. After this, this chapter provides the generalised solution of the Schrödinger equation for H atom/hydrogen-like species in which F equation, R equation, and T equations have been derived in a simple and lucid way. This chapter also deals with the Laguerre differential equation, Laguerre polynomials, Rodrigues formula for the Laguerre polynomials, Laguerre associated equation and its solution, associated Laguerre polynomials, Rodrigues formula for the associated Laguerre polynomials, and solution of the radial equation. It also provides normalisation of the radial wave function and complete wave function; for the hydrogen atom, hydrogenic atomic orbital; electron density of 1 s electron; mathematical background of shape of orbitals; the most probable distance of electron from nucleus of hydrogen atom, and average distance of electron from the nucleus of hydrogen atom. The end of this chapter describes the references and adequate computational problems (solved problems and question on concepts).
The Pauli method of quantizing the Hydrogen system using the Runge-Lenz vector is ingenious. It is well known that the energy spectrum is identical with the one obtained from the Schrödinger equation and the consistency contributed significantly to the development of Quantum Mechanics in the early days. Since the Runge-Lenz vector is a vector and it commutes with the Hamiltonian, it is natural to use it to connect energy eigenstate ∣n,l,m⟩|n,l,m\rangle∣n,l,m⟩ with other degenerate states ∣n,l±1,m′⟩|n, l\pm 1,m'\rangle∣n,l±1,m′⟩. Recursive relations can be obtained and the wave functions of the whole spectrum can be obtained easily. Note that the recursive relations are consistent with those used in factorizing the Schrödinger equation. Nevertheless, the present analysis provide a better reasoning originated from the conserved vector, the Runge-Lenz vector. As in the Pauli analysis, group theory or symmetry plays a prominent role in the present analysis, while the rest of the derivations are mostly elementary.
We add a phase variable and its corresponding operator to the description of the hydrogen atom. With the help of these additions, we device operators that act as ladder operators for the radial system. The algebra defined by the commutation relations between those operators has a Casimir operator coincident with the radial Hamiltonian of the problem. The algebra happens to be the well-known su(1,1) Lie algebra, hence the phase-dependent eigenfunctions calculated within our scheme belong in a representation of that algebra, a fact that may be useful in certain applications. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem 107: 1608 -1613, 2007