Electronic spectroscopy angular momenta

The spectroscopy of electron spin resonance (ESR) is a means of detecting direct transitions between electron Zeeman levels. The phenomenon of electron spin resonance is observed only in atomic or molecular systems having net electron spin angular momentum, that is, materials containing one or more unpaired electrons. One of the most useful parameters that can be extracted from ESR spectra is the spectral linewidth this parameter provides information on rotating correlation time (re)." ... 

In this section, we shall look at the way these various absorptions are analysed by spectroscopists. There are four kinds of quantized energy translational, rotational, vibrational and electronic, so we anticipate four corresponding kinds of spectroscopy. When a photon is absorbed or generated, we must conserve the total angular momentum in the overall process. So we must start by looking at some of the rules that allow for intense UV-visible bands (caused by electronic motion), then look at infrared spectroscopy (which follows vibrational motion) and finally microwave spectroscopy (which looks at rotation). 

As was already mentioned, in theoretical atomic spectroscopy, while considering complex electronic configurations, one has to cope with many sums over quantum numbers of the angular momentum type and their projections (3nj- and ym-coefficients). There are collections of algebraic formulas for particular cases of such sums [9, 11, 88]. However, the most general way to solve problems of this kind is the exploitation of one or another versions of graphical methods [9,11]. They are widely utilized not only in atomic spectroscopy, but also in many other domains of physics (nuclei, elementary particles, etc.) [13],... 

In practice, the transformation of any operator to irreducible form means in atomic spectroscopy that we employ the spherical coordinate system (Fig. 5.1), present all quantities in the form of tensors of corresponding ranks (scalar is a zero rank tensor, vector is a tensor of the first rank, etc.) and further on express them, depending on the particular form of the operator, in terms of various functions of radial variable, the angular momentum operator L(1), spherical functions (2.13), as well as the Clebsch-Gordan and 3n -coefficients. Below we shall illustrate this procedure by the examples of operators (1.16) and (2.1). Formulas (1.15), (1.18)—(1.22) present concrete expressions for each term of Eq. (1.16). It is convenient to divide all operators (1.15), (1.18)—(1.22) into two groups. The first group is composed of one-electron operators (1.18), the first two... 

Part 2 is devoted to the foundations of the mathematical apparatus of the angular momentum and graphical methods, which, as it has turned out, are very efficient in the theory of complex atoms. Part 3 considers the non-relativistic and relativistic cases of complex electronic configurations (one and several open shells of equivalent electrons, coefficients of fractional parentage and optimization of coupling schemes). Part 4 deals with the second-quantization in a coupled tensorial form, quasispin and isospin techniques in atomic spectroscopy, leading to new very efficient versions of the Racah algebra. 

Figure 2.2 Demonstration of the two equivalent nomenclatures used for the description of inner-shell levels and X-ray transitions (also Auger transitions, see below). The vertical direction is regarded as the energy axis (but is not to scale here). On the left-hand side is given the notation which is frequently used in inner-shell spectroscopy, on the right-hand side the corresponding single-orbital quantum numbers with n, t and j being, respectively, the principal quantum number, the orbital angular momentum and the total angular momentum which includes the spin of the electron. Also shown are the main X-ray transitions with their spectroscopic notation (for a more complete plot which includes...

Nomenclature. The spectroscopic nomenclature is directly equivalent to that used for spectroscopy X-ray, and is related to the various quantum numbers such as the principal quantum number n, the electronic quantum number 1, the total angular momentum quantum number j, and the spin quantum number s, which can take... 

One of the benefits that quantum theory has for chemistry is an improved understanding of elemental periodicity, spectroscopy and statistical thermodynamics topics which can be developed without reference to the nature of electrons, atoms or molecules. The success of these applications depend on approximations to model many-electron atoms on the hydrogen solution and the recognition of spin as a further component of electronic angular momentum, subject to the secondary condition known as (Pauli s) exclusion principle. 

Unlike a free electron, an electron in a molecule also experiences a complex interaction between spin and orbital angular momentum, spin-orbit coupling. These interactions are described in terms of a tensor, EPR spectroscopy is... 

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