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Quantum Theory of Hydrogen Atom

Z. Ficek

Published Mar 3, 2017• 0 citations
Publisher

Abstract

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.

DOI
10.1201/9781315364384-16

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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.
Bohr theory was not satisfactory as it failed to provide an interpretation of relative line intensities and splitting of spectral lines in the presence of electric field and magnetic field in the hydrogen spectrum. This theory also failed completely when it was applied to explain the energies and spectra of more complex atoms. In this chapter, we consider the application of Schrodinger wave theory to one-electron atom. The simplest one-electron system is the Hydrogen atom, whose Schrodinger equation can be exactly solved. Other one-electron system like He + , Li 2+ etc. can also be solved exactly. The chemical system with more than one-electron cannot be solved exactly due to electron-electron repulsion, which is the most problematic term.
Bohr theory was not satisfactory as it failed to provide an interpretation of relative line intensities and splitting of spectral lines in the presence of electric field and magnetic field in the hydrogen spectrum. This theory also failed completely when it was applied to explain the energies and spectra of more complex atoms. In this chapter, we consider the application of Schrödinger wave theory to one-electron atom. The simplest one-electron system is the Hydrogen atom, whose Schrödinger equation can be exactly solved. Other one-electron system like He + , Li 2+ etc. can also be solved exactly. The chemical system with more than one-electron cannot be solved exactly due to electron-electron repulsion, which is the most problematic term.
The hydrogen atom can be considered a two-particle system, an electron and a proton, with the Coulomb potential acting between them. This chapter shows how to solve the Schrodinger equation for the wave function of the two-particle system. It introduces the coordinates of the center of mass, which will allow us to split the Schrodinger equation into two independent equations, one for the center of mass motion and another for the relative motion of the electron and proton. The left- hand side of the Schrodinger equation depends solely on the spatial variables, whereas the right-hand side depends solely on time. The wave function can be written as a product of the spatial and time-dependent parts. It is very similar in form to the Schrodinger equation for the hydrogen atom except it involves two Laplacians. Since the Laplacians act on separate variables, the chapter helps to solve the Schrodinger equation using the method of separate variables.
Abstract The energies, kets and wave functions obtained from the Schrödinger equation for the hydrogen atom are examined in Chapter 9. Three quantum numbers are identified. The energies turn out to be the same as in the Bohr model, and an energy-level diagram appropriate to the quantum description is constructed. Graphs of the probability distributions are interpreted as the electron being in a “cloud” around the proton, rather than at a fixed position: the atom is fuzzy, not sharp-edged. The wavelengths of the five photons of the Balmer series are shown to be in the visible range. These photons are emitted when electrons transition from higher-excited states to the second lowest one, which means that electronic-type transitions underlie the presence of colors in our visible environment. The non-collapse of the atom, required by classical physics, is shown to arise from the structure of Schrödinger’s equation.
Even after nine decades of successful run of the Quantum Mechanics (QM), different viewpoints on foundational problems of Quantum Physics are still being actively debated. That is because mathematical logic of QM often defies the physical intuition which constitutes the main spirit of Physics. De Broglie’s hypothesis of matter waves implied that the dynamic characteristics of a micro particle in motion, can be ascribed to the wave characteristics of the wavelet accompanying the particle. The Schrödinger equation models the matter-wave interactions through wavefunction ψ and effectively serves as the foundation of QM. Even though mathematical structure of the Schrödinger equation is sound and elegant, here we show a conceptual mistake in the development of this equation wherein the physical situation has not been correctly modeled in the equation. The Coulomb potential energy of the proton electron pair in Hydrogen atom is essentially the negative interaction energy between their superposed electrostatic fields which is inversely proportional to their instantaneous separation distance. Assuming the proton to be relatively fixed at the origin of an appropriate coordinate system, the potential energy of the orbiting electron will be a function of instantaneous position coordinates of the electron. This has not been properly modeled in the Schrödinger equation. The resulting errors in the solution have been quantitatively demonstrated in this paper. We have stressed the necessity of incorporating a specific correction in the potential energy term of the Schrödinger equation, after which it may facilitate the adoption of Bohmian QM.
Certain one- and two-dimensional reductions of the three-dimensional Schrödinger equation of the hydrogen atom are considered. These reductions are carried out from the point of view of the two common sets of space coordinates: Cartesian and spherical. The resulting systems have features that relate more readily to the old quantum theory models of Bohr and Sommerfeld than the general three-dimensional hydrogen atom. Furthermore, the considerations yield interesting insights into the quantum mechanics of the hydrogen atom and may serve as helpful intermediary preparation, in an introductory presentation of the subject, for the unreduced three-dimensional case.