Electromagnetic radiation quantum theory

Planck, Max (1858-1947) A German theoretical physicist credited with foimding quantum theory— which affects all matter in the universe—Planck earned a doctoral degree at the age of twenty-one before becoming a professor at the imiversities of Kiel and Berlin. He explored electromagnetic radiation, quantum mechanics, thermodynamics, black-bodies, and entropy. He formulated the Planck constant, which describes the proportions between the energy and frequency of a photon and provides understanding of atomic strucmre. He was awarded the 1918 Nobel Prize in Physics for his discoveries. 

Quantum theory started as an explanation of electromagnetic effects (black-body radiation) in terms of corpuscular properties of light, expressed... 

A systematic development of relativistic molecular Hamiltonians and various non-relativistic approximations are presented. Our starting point is the Dirac one-fermion Hamiltonian in the presence of an external electromagnetic field. The problems associated with generalizing Dirac s one-fermion theory smoothly to more than one fermion are discussed. The description of many-fermion systems within the framework of quantum electrodynamics (QED) will lead to Hamiltonians which do not suffer from the problems associated with the direct extension of Dirac s one-fermion theory to many-fermion system. An exhaustive discussion of the recent QED developments in the relevant area is not presented, except for cursory remarks for completeness. The non-relativistic form (NRF) of the many-electron relativistic Hamiltonian is developed as the working Hamiltonian. It is used to extract operators for the observables, which represent the response of a molecule to an external electromagnetic radiation field. In this study, our focus is mainly on the operators which eventually were used to calculate the nuclear magnetic resonance (NMR) chemical shifts and indirect nuclear spin-spin coupling constants. 

Radiation is fundamentally different from conduction as it describes the transfer of heat between two substances that are not in contact with each other. Like conduction, radiation is an independent form of heat transfer. Ignoring the conflicts of wave and quantum theory, radiation, refers to the transmission of electromagnetic energy through space. 

The interaction processes between UV-Vis photons and the outer electrons of the atoms of the analytes can be understood using quantum mechanics theory. In the thermodynamic equilibrium between matter and interacting electromagnetic radiation, according to the radiation laws postulated by Einstein, three basic processes between two stable energy levels 1 and 2 are possible. These processes, which can be defined by their corresponding transition probabilities, are summarised in Figure 1.3. 

Transition probabilities. The interaction of quantum systems with light may be studied with the help of Schrodinger s time-dependent perturbation theory. A molecular complex may be in an initial state i), an eigenstate of the unperturbed Hamiltonian, Jfo I ) = E 10- If the system is irradiated by electromagnetic radiation of frequency v = co/2nc, transitions to other quantum states /) of the complex occur if the frequency is sufficiently close to Bohr s frequency condition,... 

We now consider the effect of exposing a system to electromagnetic radiation. Our treatment will involve approximations beyond that of replacing (3.13) with (3.16). A proper treatment of the interaction of radiation with matter must treat both the atom and the radiation field quantum-mechanically this gives what is called quantum field theory (or quantum electrodynamics). However, the quantum theory of radiation is beyond the scope of this book. We will treat the atom quantum-mechanically, but will treat the radiation field as a classical wave, ignoring its photon aspect. Thus our treatment is semiclassical. 

This is due to the comparative weakness of the electromagnetic interaction, the theory of which contains a small dimensionless parameter (fine structure constant), by the powers of which the corresponding quantities can be expanded. The electron transition probability of the radiation of one photon, characterized by a definite value of angular momentum, in the first order of quantum-electrodynamical perturbation theory mdy be described as follows [53] (a.u.) ... 

A full explanation of the properties of light requires both the wave theory of electromagnetic radiation and the quantum theory. Most photochemical processes are best understood in terms of the quantum theory, which says that light is made up of discrete particles called quanta or photons. Each quantum carries an amount of energy, S, determined by the wavelength of the light, A. Equation 13.1, in which h is Planck s constant and c is the speed of light in a vacuum,... 

There are several reasons for starting this account with a discussion of electromagnetic radiation. Historically, it was in this area that the quantum theory first developed. It is easier here to understand the evidence for the theory, and to appreciate some of its paradoxical consequences, than it is in the quantum theory of matter. The applications of the light-quantum hypothesis, as it was first called, also provide key pieces of evidence for the quantization of energy in atoms and molecules. Studies of the absorption and emission of radiation—the field of spectroscopy—and of the effect of light on chemical reactions—photochemistry—are very important areas of modem chemistry, in which the quantum nature of radiation is crucial. 

It turns out that electromagnetic waves exhibit properties of both waves and particles, or equally valid, electromagnetic waves are neither waves nor particles. This fundamental paradox is at the heart of quantum theory. You can perform experiments that unequivocally demonstrate light is definitely a wave. You can also perform experiments that unequivocally demonstrate light is definitely a particle. Nonetheless, there is one important relationship that allows the energy of electromagnetic radiation to be calculated if the frequency or wavelength is known ... 

The theory gives rise to a concept of atomic or molecular orbital, ie the wave-function, which depends explicitly on the spatial coordinates of only one electron and the quantum numbers that define energy, spin, orbital momentum, and symmetry properties of the two last wavefunctions. Quantum numbers of the wavefunc-tions in lower and upper states determine the possible interaction of the entity with electromagnetic radiation [1],... 

The interaction between electromagnetic radiation and atoms or molecules is now discussed by empirical methods, then by semiclassical arguments, and finally by quantum theory. 

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