Light quantum mechanics

So far, our quantum mechanics examples have been rather far afield from questions of immediate interest to our study of solids. In particular, we aim to see what light quantum mechanics sheds on the origin of bonding and cohesion in solids. To do so, in this introductory chapter we consider two opposite extremes. Presently, we consider the limit in which each atom is imagined to donate one or more electrons to the solid which are then distributed throughout the solid. The resulting model is the so-called electron gas model and will be returned to repeatedly in coming... 

The view of this author is that knowledge of the internal molecular motions, perhaps as outlined in this chapter, is likely to be important in achieving successfiil control, in approaches that make use of coherent light sources and quantum mechanical coherence. However, at this point, opinions on these issues may not be much more than speculation. 

A diagrannnatic approach that can unify the theory underlymg these many spectroscopies is presented. The most complete theoretical treatment is achieved by applying statistical quantum mechanics in the fonn of the time evolution of the light/matter density operator. (It is recoimnended that anyone interested in advanced study of this topic should familiarize themselves with density operator fonnalism [8, 9, 10, H and f2]. Most books on nonlinear optics [13,14, f5,16 and 17] and nonlinear optical spectroscopy [18,19] treat this in much detail.) Once the density operator is known at any time and position within a material, its matrix in the eigenstate basis set of the constituents (usually molecules) can be detennined. The ensemble averaged electrical polarization, P, is then obtained—tlie centrepiece of all spectroscopies based on the electric component of the EM field. 

Technology developments are revolutionizing the spectroscopic capabilities at THz frequencies. While no one teclmique is ideal for all applications, both CW and pulsed spectrometers operating at or near the fiindamental limits imposed by quantum mechanics are now within reach. Compact, all-solid-state implementations will soon allow such spectrometers to move out of the laboratory and into a wealth of field and remote-sensing applications. From the study of the rotational motions of light molecules to the large-amplitude vibrations of... 

Altliough a complete treatment of optical phenomena generally requires a full quantum mechanical description of tire light field, many of tire devices of interest tliroughout optoelectronics can be described using tire wave properties of tire optical field. Several excellent treatments on tire quantum mechanical tlieory of tire electromagnetic field are listed in [9]. 

Besides the intrinsic usefulness of Fourier series and Fourier transforms for chemists (e.g., in FTIR spectroscopy), we have developed these ideas to illustrate a point that is important in quantum chemistry. Much of quantum chemistry is involved with basis sets and expansions. This has nothing in particular to do with quantum mechanics. Any time one is dealing with linear differential equations like those that govern light (e.g. spectroscopy) or matter (e.g. molecules), the solution can be written as linear combinations of complete sets of solutions. 

Quantum mechanical calculations generally have only one carbon atom type, compared with the many types of carbon atoms associated with a molecular mechanics force field like AMBER. Therefore, the number of quantum mechanics parameters needed for all possible molecules is much smaller. In principle, very accurate quantum mechanical calculations need no parameters at all, except fundamental constants such as the speed of light, etc. 

Classical and Quantum Mechanics. At the beginning of the twentieth century, a revolution was brewing in the world of physics. For hundreds of years, the Newtonian laws of mechanics had satisfactorily provided explanations and supported experimental observations in the physical sciences. However, the experimentaUsts of the nineteenth century had begun delving into the world of matter at an atomic level. This led to unsatisfactory explanations of the observed patterns of behavior of electricity, light, and matter, and it was these inconsistencies which led Bohr, Compton, deBroghe, Einstein, Planck, and Schrn dinger to seek a new order, another level of theory, ie, quantum theory. 

Electrons are very light particles and cannot be described by classical mechanics. They display both wave and particle characteristics, and must be described in terms of a wave function, T. Tlie quantum mechanical equation corresponding to Newtons second law is the time-dependent Schrbdinger equation (h is Plancks constant divided by 27r). 

If we are interested in describing the electron distribution in detail, there is no substitute for quantum mechanics. Electrons are very light particles, and they cannot be described even qualitatively correctly by classical mechanics. We will in this and subsequent chapters concentrate on solving the time-independent Schrodinger equation, which in short-hand operator fonn is given as... 

Since quantum mechanics allows us to predict, with certainty, the component of the second spin by measuring the same spin component of the first (and remotely positioned) particle - and to do so without in any way disturbing that second particle - BPR s first two assumptions attribute an element of physical reality to the value of any spin component of either particle i.e. the spin components must be determinate. On the other hand, assuming that the particles cannot communicate information any faster than at the speed of light, the only way to stay consistent with BPR s third postulate is to assume the existence of hidden variables. 

Scientists in the 1920s, speculating on this problem, became convinced that an entirely new approach was required to treat electrons in atoms and molecules. In 1924 a young French scientist, Louis de Broglie (1892-1987), in his doctoral thesis at the Sorbonne made a revolutionary suggestion. He reasoned that if light could show the behavior of particles (photons) as well as waves, then perhaps an electron, which Bohr had treated as a particle, could behave like a wave. In a few years, de Broglie s postulate was confirmed experimentally. This led to the development of a whole new discipline, first called wave mechanics, more commonly known today as quantum mechanics. 

In the light of your answer, point out erroneous features of the following models of a hydrogen atom (both of which were used before quantum mechanics demonstrated their inadequacies). 

The quantum mechanical view of Raman scatering sees a radiation field hvo inducing a transition from a lower level A to a level n. If vnlc is the transition frequency, then the inelastically scattered light has frequency v0 — v t. That is, the molecule removes energy hv k from an incident photon. This process corresponds to Stokes scattering. Alternatively, a molecule under-... 

The third common level is often invoked in simplified interpretations of the quantum mechanical theory. In this simplified interpretation, the Raman spectrum is seen as a photon absorption-photon emission process. A molecule in a lower level k absorbs a photon of incident radiation and undergoes a transition to the third common level r. The molecules in r return instantaneously to a lower level n emitting light of frequency differing from the laser frequency by —>< . This is the frequency for the Stokes process. The frequency for the anti-Stokes process would be + < . As the population of an upper level n is less than level k the intensity of the Stokes lines would be expected to be greater than the intensity of the anti-Stokes lines. This approach is inconsistent with the quantum mechanical treatment in which the third common level is introduced as a mathematical expedient and is not involved directly in the scattering process (9). 

The axiomatic way of teaching quantum mechanics (QM) is anaiyzed in the light of its effectiveness in making students ready to understand and use QM. A more intuitive method of teaching QM is proposed. An outline of how a course implementing that method could be structured is presented. 

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