Wave function quantum theory

The quantum phase factor is the exponential of an imaginary quantity (i times the phase), which multiplies into a wave function. Historically, a natural extension of this was proposed in the fonn of a gauge transformation, which both multiplies into and admixes different components of a multicomponent wave function [103]. The resulting gauge theories have become an essential tool of quantum field theories and provide (as already noted in the discussion of the YM field) the modem rationale of basic forces between elementary particles [67-70]. It has already been noted that gauge theories have also made notable impact on molecular properties, especially under conditions that the electronic... 

The gradient of the PES (force) can in principle be calculated by finite difference methods. This is, however, extremely inefficient, requiring many evaluations of the wave function. Gradient methods in quantum chemistiy are fortunately now very advanced, and analytic gradients are available for a wide variety of ab initio methods [123-127]. Note that if the wave function depends on a set of parameters X], for example, the expansion coefficients of the basis functions used to build the orbitals in molecular orbital (MO) theory. 

The functions are known as the angular wave functions or, because they describe the distribution of p over the surface of a sphere of radius r, spherical harmonics. The quantum number n = l,2,3,...,oo and is the same as in the Bohr theory, is the azimuthal quantum number associated with the discrete orbital angular momentum values, and is... 

There will be many occasions when we shall need to multiply symmetry species or, in the language of group theory, to obtain their direct product. For example, if H2O is vibrationally excited simultaneously with one quantum each of Vj and V3, the symmetry species of the wave function for this vibrational combination state is... 

In 1913 Niels Bohr proposed a system of rules that defined a specific set of discrete orbits for the electrons of an atom with a given atomic number. These rules required the electrons to exist only in these orbits, so that they did not radiate energy continuously as in classical electromagnetism. This model was extended first by Sommerfeld and then by Goudsmit and Uhlenbeck. In 1925 Heisenberg, and in 1926 Schrn dinger, proposed a matrix or wave mechanics theory that has developed into quantum mechanics, in which all of these properties are included. In this theory the state of the electron is described by a wave function from which the electron s properties can be deduced. 

Another consequence of the quantum theory of the atomic and nuclear systems is that no two protons, or two neutrons, can have exactly the same wave function. The practical appHcation of this rule is that only a specific number of particles can occupy any particular atomic or nuclear level. This prevents all of the electrons of the atom, or protons and neutrons in the nucleus, from deexciting to the single lowest state. 

MaxweU-Boltzmaim particles are distinguishable, and a partition function, or distribution, of these particles can be derived from classical considerations. Real systems exist in which individual particles ate indistinguishable. Eor example, individual electrons in a soHd metal do not maintain positional proximity to specific atoms. These electrons obey Eermi-Ditac statistics (133). In contrast, the quantum effects observed for most normal gases can be correlated with Bose-Einstein statistics (117). The approach to statistical thermodynamics described thus far is referred to as wave mechanics. An equivalent quantum theory is referred to as matrix mechanics (134—136). 

It is clear that the density matrix formalism renders a considerable simplification of the basis for the quantum theory of many-particle systems. It emphasizes points of essential physical and chemical interests, and it avoids more artificial or conventional ideas, as for instance different types of basic orbitals. The question is, however, whether this formalism can be separated from the wave function idea itself as a fundament. Research on this point is in progress, and one can expect some interesting results within the next few years. 

The structural interpretation of the principal quantum number of nucleonic orbital wave functions and the structural basis provided by the close-packed-spheron theory for the neutron and proton magic numbers are discussed in notes submitted to Phys. Rev. Letters and Nature (L. Pauling, 1965). 

The shell theory has had great success in accounting for many nuclear properties (3). The principal quantum number n for nucleons is usually taken to be n, + 1, where nr, the radial quantum number, is the number of nodes in the radial wave function. (For electrons n is taken to be nr + / +1 / is the azimuthal quantum number.) Strong spin-orbit coupling is assumed,... 

Quantum theory was developed during the first half of the twentieth century through the efforts of many scientists. In 1926, E. Schrbdinger inteijected 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. Schrodinger 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. Several experiments, which lead to a physical interpretation of the wave function, are also described. In Chapter 2, the Schrodinger differential wave equation is introduced and the wave function concept is extended to include particles in an external potential field. The formal mathematical postulates of quantum theory are presented in Chapter 3. 

Another experiment that relates to the physical interpretation of the wave function was performed by O. Stem and W. Gerlach (1922). Their experiment is a dramatic illustration of a quantum-mechanical effect which is in direct conflict with the concepts of classical theory. It was the first experiment of a non-optical nature to show quantum behavior directly. 

In comparing the two experiments with both slits open, we see that interacting with the system by placing a detector at slit A changes the wave function of the system and the experimental outcome. This feature is an essential characteristic of quantum theory. We also note that without a detector at slit A, there are two indistinguishable ways for the particle to reach the detection screen D and the two wave functions and are added together. 

In this section we state the postulates of quantum mechanics in terms of the properties of linear operators. By way of an introduction to quantum theory, the basic principles have already been presented in Chapters 1 and 2. The purpose of that introduction is to provide a rationale for the quantum concepts by showing how the particle-wave duality leads to the postulate of a wave function based on the properties of a wave packet. Although this approach, based in part on historical development, helps to explain why certain quantum concepts were proposed, the basic principles of quantum mechanics cannot be obtained by any process of deduction. They must be stated as postulates to be accepted because the conclusions drawn from them agree with experiment without exception. 

Prior to Dirac s relativistic quantum theory, W. Pauli (1927) showed how spin could be incorporated into non-relativistic quantum mechanics. Since the subject of relativistic quantum mechanics is beyond the scope of this book, we present in this chapter Pauli s modification of the wave-function description so... 

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