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Proceedings of the National Academy of Sciences

Discrete wave mechanics: The hydrogen atom

Frederick T. Wall

Published Aug 1, 1986• 9 citations
Publisher

Abstract

The quantum mechanical problem of the hydrogen atom is treated by use of a finite difference equation in place of Schrödinger's differential equation. The exact solution leads to a wave vector energy expression that is readily converted to the Bohr-Rydberg formula. (The calculations here reported are limited to spherically symmetric states.) The wave vectors reduce to the familiar solutions of Schrödinger's equation as c --> infinity. The internal consistency and limiting behavior provide support for the view that the equations employed could well constitute an approach to a relativistic formulation of wave mechanics.

DOI
10.1073/pnas.83.16.5753

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The quantum mechanical problem of the hydrogen atom is treated by use of a finite difference equation in place of Schrödinger's differential equation. The exact solution leads to a wave vector energy expression that is readily converted to the Bohr-Rydberg formula. (The calculations here reported are limited to spherically symmetric states.) The wave vectors reduce to the familiar solutions of Schrödinger's equation as c --> infinity. The internal consistency and limiting behavior provide support for the view that the equations employed could well constitute an approach to a relativistic formulation of wave mechanics.
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A discrete wave mechanical treatment of the hydrogen atom is extended to deal with states involving nonzero angular momentum. Only the radial portions of the wave vectors are covered. It is predicted that there is a nonzero minimum distance between the electron and the nucleus; this threshold distance increases with increasing angular momentum. Appropriate finite difference equations are formulated. The states with angular momentum exhibit the same degeneracy as do corresponding energy levels obtained from solutions of Schrödinger's equation.
This chapter considers Schrodinger's model of hydrogen atom and analyzes in details the quantum wave mechanics approach to the motion of the electron in the hydrogen atom. The stationary Schrodinger equation is not easy to solve as it stands, and the whole problem looks rather complicated when expressed in terms of Cartesian coordinates. An essential difference between Bohr's and Schrodinger's models is that there are three quantum numbers, n , l , m , rather than the one number n describing a state of the electron. Moreover, in Bohr's model the atom is, at each instant, in one and only one energy state, that is., at each instant, the state of the atom is definite, but according to Schrodinger's model, the atom can exist in a superposition of states. In other words, the atom can be simultaneously in more than one energy state at a given instant. This is clearly incompatible with Bohr's model.
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).
There are certain prime features of physical systems—notably rotation and its associated angular momentum—that simply do not appear in a one-dimensional world. This chapter introduces the three-dimensional Schrodinger equation and applies it to the analysis of a particle in a three-dimensional box and to the spherically symmetric wave functions of hydrogen. The time-independent Schrodinger equation can be viewed in a way that gives it a family resemblance to many other differential equations of physics, and which expresses its structure in very general terms. A computer solution uses dimensionless variables based on natural units. The Schrodinger theory does not have the limitations of the Bohr theory. Schrodinger theory incorporates the well-established wave nature of matter and can be generalized to analyze systems for which the Bohr theory has proven inadequate: multi-electron atoms, chemical properties of atoms, molecular and solid-state physics and chemistry, as well as more subtle effects in hydrogen itself.
This paper discusses the relativistic Schrödinger differential wave equation for the hydrogen atom and hydrogen-like cations, which have measured ionization energies from hydrogen to the Cu 28+ hydrogen-like cation.The analytical solution to the relativistic Schrödinger differential wave equation correlates with experimental data if the angular momentum quantum number l >0.For quantum levels with l = 0 , the analytical solutions predict ionization energy values larger than that measured for the hydrogen atom and hydrogen-like cations.Also, beyond the element erbium, Z > 68 for l=0 quantum states, the analytical solution yields energy values that are complex numbers.This is similar for the Dirac relativistic differential wave equation which fails for nuclei that have an atomic number larger than 137.Using measured 1s ionization energy values of hydrogen-like cations, a numerical solution to the relativistic Schrödinger differential wave equation is possible since an analytical one is not when the measured ionization energy is different from the analytical result.In addition, since the analytical solutions to the radial part of the relativistic Schrödinger differential wave equation are complicated, normalized numerical solutions are less difficult to obtain using Microsoft Excel.Most differential equations do not have analytical solutions, and, therefore, only numerical solutions are possible utilizing boundary or initial conditions. Classical Schrödinger Differential Wave Equation and Wave-Particle Duality in Quantum Mechanics