Because atoms and molecules are small, their behavior can only be understood using quantum mechanics, rather than classical mechanics. Quantum mechanics amounts to studying the behavior of electrons and nuclei and their interactions. We will limit ourselves to slowly moving electrons and nuclei, and thus will not need to discuss relativistic quantum mechanics. Large particles also obey quantum mechanics, but the relevant wavelengths are so small that we don't notice them. Small particles absolutely require the use of quantum mechanics for any meaningful understanding. This treatment is not merely an inconvenience: it leads to useful and interesting phenomena such as the Pauli exclusion principle, the Aufbau principle, Hund's rules, the Heisenberg uncertainty principle, wave-particle duality, the photoelectric effect, Ehrenfest's theorem, and the correspondence principle.
Because atoms and molecules are small, their behavior can only be understood using quantum mechanics, rather than classical mechanics. Quantum mechanics amounts to studying the behavior of electrons and nuclei and their interactions. We will limit ourselves to slowly moving electrons and nuclei, and thus will not need to discuss relativistic quantum mechanics. Large particles also obey quantum mechanics, but the relevant wavelengths are so small that we don't notice them. Small particles absolutely require the use of quantum mechanics for any meaningful understanding. This treatment is not merely an inconvenience: it leads to useful and interesting phenomena such as the Pauli exclusion principle, the Aufbau principle, Hund's rules, the Heisenberg uncertainty principle, wave-particle duality, the photoelectric effect, Ehrenfest's theorem, and the correspondence principle.
The objective of this chapter is to go over a few of the basic concepts of quantum mechanics in preparation for a discussion of spectroscopy, which is in many ways the business end of quantum mechanics, at least for chemical scientists. We will also need a few quantum mechanical ideas from time to time in our study of thermodynamics and of kinetics. Why should we learn quantum mechanics at all? Atoms and molecules are small, and their constituent parts, electrons, protons and neutrons, are even smaller. Early in the twentieth century, we learned that small things don't obey the laws of classical mechanics. A different kind of mechanics, quantum mechanics, is required to understand chemistry on a fundamental level. In fact, we need different mechanical theories to treat extremes of both size and speed. Figure 2.1 summarizes the situation. There isn't a sharp cut-off between the various sectors of this diagram. Also note that some of the theories are more general than others. We could in principle use quantum mechanics or general relativity to predict the trajectories of tennis balls, but it just isn't worth the effort, given that classical mechanics works perfectly well in this range of masses and speeds. On the other hand, classical mechanics doesn't give very good results for things that are either extremely large, or small, or fast. Like it or not, to discuss phenomena on an atomic scale, we need quantum mechanics. Ordinary (non-relativistic) quantum mechanics is generally adequate, although electrons in heavy atoms sometimes reach relativistic speeds (approaching the speed of light, c ), requiring relativistic quantum mechanics.
Classical mechanics, which gives a fairly accurate description of large systems (e.g., solar system) as also of mechanical systems in our every day life, however, breaks down when applied to small (microscopic) systems such as molecules, atoms and nuclei. For example, (1) classical mechanics cannot even explain why the atoms are stable at all. A classical atom with electrons moving in circular or elliptic orbits around the nucleus would continuously radiate energy in the form of electromagnetic radiation because an accelerated charge does radiate energy. As a result the radius of the orbit would become smaller and smaller, resulting in instability of the atom. On the other hand, the atoms are found to be remarkably stable in practice. (2) Another fact of observation that classical mechanics fails to explain is wave particle duality in radiation as well as in material particles. It is well known that light exhibits the phenomena of interference, diffraction and polarization which can be easily understood on the basis of wave aspect of radiation. But light also exhibits the phenomena of photo-electric effect, Compton effect and Raman effect which can only be understood in terms of corpuscular or quantum aspect of radiation. The dual behavior of light, or radiation cannot be consistently understood on the basis of classical concepts alone or explained away by saying that light behaves as wave or particle depending on the kind of experiment we do with it (complementarity). Moreover, a beam of material particles, like electrons and neutrons, demonstrates wave-like properties (e.g., diffraction). A brief outline of phenomena that require quantum mechanics for their understanding follows.
Quantum mechanics is a theory to explain and predict the behavior of particles such as electrons, protons, neutrons, atomic nuclei, atoms, and molecules, as well as the photon–the particle associated with electromagnetic radiation or light. From quantum theory we obtain the laws of chemistry as well as explanations for the properties of materials, such as crystals, semiconductors, superconductors, and superfluids. Applications of quantum behavior give us transistors, computer chips, lasers, and masers. The relatively new field of molecular biology, which leads to our better understanding of biological structures and life processes, derives from quantum considerations. Thus, quantum behavior encompasses a large fraction of modern science and technology. Quantum theory was developed during the first half of the twentieth century through the efforts of many scientists. In 1926, E. Schrödinger interjected wave mechanics into the array of ideas, equations, explanations, and theories that were prevalent at the time to explain the growing accumulation of observations of quantum phenomena. His theory introduced the wave function and the differential wave equation that it obeys. Schrödinger's wave mechanics is now the backbone of our current conceptional understanding and our mathematical procedures for the study of quantum phenomena. Our presentation of the basic principles of quantum mechanics is contained in the first three chapters. Chapter 1 begins with a treatment of plane waves and wave packets, which serves as background material for the subsequent discussion of the wave function for a free particle.
The behavior of classical macroscopic particles – from baseballs to planets – is governed by Newtonian mechanics as we have described in the first chapters of this book. The behavior of very small particles, on the other hand, is governed by an entirely different collection of equations and rules that go under the name of “quantum mechanics” and these particles are referred to as quantum particles. These rules have analogies to classical mechanics, but are fundamentally different and somewhat mysterious as we discussed in Chapter 8. The fundamental principles of quantum mechanics cannot be proven to be correct. They were developed based on the results of experimental observation, by analogy with classical mechanics, and through the consideration of logical implications of the formalisms used. There is no way to derive the fundamental elements of quantum mechanics, any more than one could predict from first principles that Newtonian forces should add as vectors. On the other hand, quantum mechanics is among the most rigorously tested theories in science, and the predictions of quantum mechanics have, so far, always been in agreement with experiment. In this chapter, we will present quantum mechanics as a series of postulates and examine their implications in application to simple one-dimensional systems. In the next chapter we will examine quantum effects in real systems including atoms, molecules, crystals, and artificially engineered nano-structures. Postulates of quantum mechanics QM Postulate 1: A quantum particle is described by a wave function Ψ( x , y , z , t ) which is a function of spatial coordinates and time. All physically determinable quantities can be derived from the wave function Ψ( x , y , z , t ) ; quantities which cannot be found from the wave function are not physically meaningful. Note that some things that one could ask about a quantum particle, for example the exact position and simultaneous exact momentum of a particle, are not derivable from the wave function and are therefore considered indeterminate (or uncertain ). These are things which cannot ever be known about a particle, and, as such, they are meaningless to contemplate.
New interpretation of the atomic spectra and other quantum phenomena: A mixed mechanism of classical LC circuits and quantum wave-particle duality
We study the energy conversion laws of the macroscopic harmonic $LC $ oscillator, the electromagnetic wave (photon) and the hydrogen atom. As our analysis indicates that the energies of these apparently different systems obey exactly the same energy conversion law. Based on our results and the wave-particle duality of electron, we find that the atom in fact is a natural microscopic LC oscillator. In the framework of classical electromagnetic field theory we analytically obtain, for the hydrogen atom, the quantized electron orbit radius. Without the adaptation of any other fundamental principles of quantum mechanics, we present a reasonable explanation of the polarization of photon, the Zeeman effect, Selection rules and Pauli exclusion principle. Particularly, it is found that a pairing Pauli electron can move closely and steadily in a DNA-like double helical electron orbit. Our results also reveal an essential connection between electron spin and the intrinsic helical movement of electron and indicate that the spin itself is the effect of quantum confinement. In addition, a possible physical mechanism of superconductivity and the deeper physical understandings of the electron mass, zero point energy, and the hardness property of electron are also provided. Finally, we show analytically that the Dirac's quantization of magnetic monopole is merely a special handed electron at absolute zero-temperature, which strongly suggests that any efforts to seek for the magneticmonopole in real space will be entirely in vain. Furthermore, it appears that the electron's spin and the magnetic monopole are actually two different concepts for one possible physical phenomenon.