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of Bits and Bonds: Hi-Tech Methods Predict the Newest Molecules: Part 2. Quantization

Anne‐Frances Miller

Published Jan 1, 2013• 0 citations
OpenAlex

Abstract

A quick tour through the development of Bohr’s model of the atom concludes with calculation of the allowable (quantized) energies of an electron orbiting in a Hydrogen atom. Electron states, and transitions between states are presented, as are their related spectra.

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The electronic transition energies from the electron clouds are the same as predicted by the Bohr model. The hydrogen atom, most probable radius of the first quantum mechanical electron cloud is identical to the radius of the first Bohr orbit. The quantum mechanical description goes much further, however. Not only does it predict a series of increasingly larger spherical electron clouds, but other electron cloud series as well. Because of their three dimensional shapes, these electron clouds sometimes are said to describe space states. The analogy to planetary orbits ends when we grasp the fact that quantum mechanical electron clouds are three-dimensional, where a Bohr orbit would be a circle lying entirely in a plane. Quantum mechanics also predicts the ionization energy of the hydrogen atom.
The existence of line spectra can be explained bymeans of the first “quantum”model of the atom, developed by Bohr in 1913. Although the Bohr model of the hydrogen atom was eventually replaced, it yields the correct values for the observed spectral lines, and gives a substantial insight into the structure of atoms in general. The following derivation has the objective of obtaining the energy levels of the Bohr atom. If we can obtain the energy levels, we can reproduce the hydrogen atom spectra. The derivation proceeds with three major elements: first, use force balance to relate the velocity to the radius of the electron orbit, then use a quantum assumption to get the radius, then solve for the energies.
The mere existence of stable atoms, and their arrangement into many-atom nanoscale structures, can only be explained by the laws of quantum mechanics. Indeed, the accumulated evidence regarding the internal structure of atoms motivated the formulation of quantum mechanics at the early twentieth century. Here we focus on single-electron (hydrogen-like) atoms. The dominance of the Coulomb central potential between the electron and nucleus, translates into a simple Schrödinger equation for their relative position distribution. Solving rigorously this equation reveals quantized energy levels, which explains the emission spectra of hydrogen-like atoms (Rydberg formula). The corresponding stationary probability density distributions for the electron around the nucleus are reminiscent of the Bohr model, where classical trajectories (orbits) are replaced by single-electron wave functions (orbitals). The degeneracies of different orbitals, associated with three quantum numbers, will later turn out to be critical for understanding many-electron atoms and the periodic table of the elements.
Niels Bohr constructed the first version of quantum mechanics. It has been called “old quantum mechanics” with a connotation of being obsolete. It is logically consistent, however, and deserves the name of simple quantum mechanics (SQM). It differs only from the semiclassical approximation by assuming that the average position and average velocity of an electron can be sharply defined on closed orbits. This assumption does not contradict Heisenberg’s uncertainty relations, since the quantization rule means that the electron can be anywhere on this orbit when it allows for stationary waves. This approach was remarkably efficient for one electron in hydrogen atoms and even for the electron pair in hydrogen molecules. However, dissociation of H2 and determination of the orbit of the single electron in H 2 + led to problems that remained unsolved for more than 100 years. Their solution, presented here, yields more physical insight and reveals, for instance, that mutual polarization of two hydrogen atoms can yield a metastable state.
In the 1920s, the old quantum theory was gradually being superseded by the new quantum theory. The cornerstone of the old theory was Bohr’s model of the hydrogen atom which predicted that an electron cannot orbit the proton in the hydrogen atom in any arbitrary fashion. Orbits are “quantized”, meaning that only certain sizes, shapes and magnetic properties are allowed. The principal quantum number n determined the allowed radii of the orbits, the orbital quantum number l determined the allowed shapes, and the magnetic quantum number m determined the magnetic behavior. Additionally, there is a fourth quantum number s which denotes the fact that the electron has an additional angular momentum, loosely associated with self rotation about its own axis, and that is quantized in units of (1/2). The old quantum theory was useful to infer the existence of discrete energy levels in atoms, calculate energy spacings between these levels, and therefore allowed one to interpret atomic spectra.