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Proceedings of the National Academy of Sciences

Wave Mechanics and the Normal State of the Hydrogen Molecule

E. U. Condon

Published Jun 1, 1927• 38 citations
Publisher

Abstract

The problem of the motion of a particle attracted by two fixed centers of force according to the Coulomb force law can be treated by classical mechanics and has been used in quantum theory by Pauli and Messen for a theory of the hydrogen molecule ion.1 In the quantum mechanics, where the energy levels are determined as the “eigenwerte” of Schrodinger’s equation, the variables are separable and the boundary value problem is easily set up. But thus far a satisfactory treatment of the differential equations involved is lacking. Burrau2 has recently carried out a numerical integration of the problem for the lowest energy level of an electron moving under the influence of two fixed centers of Coulomb attraction as a function of the distance apart of these centers. In this paper, Burrau’s data are used to give a semi-quantitative discussion of the neutral hydrogen molecule. His values are: Nuclear separation 1.0 1.3 1.6 1.8 2.0 2.2 2.4 2.95 Electronic energy 2.896 2.648 2.436 2.309 2.204 2.109 2.025 1.836 The unit of separation is the Bohr l1 orbit radius of hydrogen atom, that of energy is the ionization potential of atomic hydrogen.

DOI
10.1073/pnas.13.6.466

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The problem of the motion of a particle attracted by two fixed centers of force according to the Coulomb force law can be treated by classical mechanics and has been used in quantum theory by Pauli and Messen for a theory of the hydrogen molecule ion.1 In the quantum mechanics, where the energy levels are determined as the “eigenwerte” of Schrodinger’s equation, the variables are separable and the boundary value problem is easily set up. But thus far a satisfactory treatment of the differential equations involved is lacking. Burrau2 has recently carried out a numerical integration of the problem for the lowest energy level of an electron moving under the influence of two fixed centers of Coulomb attraction as a function of the distance apart of these centers. In this paper, Burrau’s data are used to give a semi-quantitative discussion of the neutral hydrogen molecule. His values are:
Nuclear separation
1.0
1.3
1.6
1.8
2.0
2.2
2.4
2.95
Electronic energy
2.896
2.648
2.436
2.309
2.204
2.109
2.025
1.836
The unit of separation is the Bohr l1 orbit radius of hydrogen atom, that of energy is the ionization potential of atomic hydrogen.
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.
The hydrogen atom is the Rosetta stone of the early twentieth century atomic physics. The attempt to decipher its structure and properties led to the development of quantum mechanics and the unraveling of many of the mysteries of atomic, molecular, and solid state physics, and a good deal of chemistry and modern biology. Unlike the various one-dimensional model problems that we have been studying in the previous chapters, the hydrogen atom is a real physical system in three dimensions. It consists of an electron moving in a spherically symmetric potential well due to the Coulomb attraction of the positively charged nucleus. In three dimensions, the electron is not constrained to move linearly. It can execute orbital motions and, thus, has angular momentum. Not only is the total energy of the electron in the atom quantized, its angular momentum also has interesting and unexpected quantized properties that cannot possibly be understood on the basis of classical mechanics and electrodynamics. They are, however, the natural and necessary consequences of the basic postulates of quantum mechanics, as will be shown in this chapter. According to classical mechanics and electrodynamics, it is not possible to have a stable structure consisting of a small positively charged nucleus at the center of an electrically neutral atom with an electron sitting in its vicinity. For the electron not to be attracted into the positive charge, it must be orbiting around the nucleus so that the centrifugal force will counter the Coulomb attraction of the nucleus and maintain a constant electron orbit.
This chapter presents a detailed analysis of the hydrogen-like atom within the framework of quantum mechanics. The radial Schrödinger equation is solved for the Coulomb potential, yielding the quantized energy spectrum, energy eigenstates, and the associated degeneracy of levels. The expectation value of the electron's radius is calculated, and a comparison is drawn between quantum predictions and classical circular orbits. The quantum two-body problem is introduced to account for the motion of the nucleus, revealing its influence on the energy levels of the electron. This correction underpins the operation of the mass spectrometer and supports the spectroscopic identification of hydrogen isotopes such as deuterium and tritium. The analysis also explains how similar effects confirm the presence of helium in the solar spectrum through astrophysical observations. Metadata/Keywords: hydrogen-like atom, Coulomb potential, energy spectrum, quantum orbits, nucleus motion, two-body problem, mass spectrometer, hydrogen isotopes, helium, solar spectrum
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.
The hydrogen molecular ion and the hydrogen molecule are treated in an approximate calculation based on classical electrodynamics which includes classical zero-point radiation. It is found within the classical theory that a molecular ion is less-well bound than a hydrogen atom plus a distant proton. The smaller binding energy is explained due to the repulsive nature of the force between the proton and the atom when considering the most natural resonant orbit of the electron. The approximate classical electromagnetic calculation gives a binding energy of 2.1eV2.1eV2.1eV and a proton separation of 0.916Ao0.916A^{o}0.916Ao for the hydrogen molecular ion. The hydrogen molecule is formed by adding a single additional electron to the ion. The electrostatic attraction of the electron to the ion gives a binding energy of 4.6eV4.6eV4.6eV and a inter-proton separation of 0.6Ao0.6A^{o}0.6Ao for the hydrogen molecule in this classical electromagnetic approximation.
This chapter illustrates Niels Bohr's ideas in some detail. In the formulation of his model, Bohr assumed that the electron in the hydrogen atom moves under the influence of the Coulomb attraction between it and the positively charged nucleus, as assumed in classical mechanics. The Bohr model was very successful in explaining the discrete atomic spectra of one-electron atoms. The Bohr model is, of course, a theoretical model of an atom. Using Bohr's quantization postulate, find the linear velocity of the electron's sphere. To find the radius of the orbit, Bohr postulated that the angular momentum of the electron is quantized, i.e., it can only take values that are integer multiples of ħ. The chapter begins with considering the classical equation of motion for the electron in a circular orbit, which is based on Newton's laws of motion and Coulomb's law of electric force.