Quantum numbers properties

Electrons, protons and neutrons and all other particles that have s = are known as fennions. Other particles are restricted to s = 0 or 1 and are known as bosons. There are thus profound differences in the quantum-mechanical properties of fennions and bosons, which have important implications in fields ranging from statistical mechanics to spectroscopic selection mles. It can be shown that the spin quantum number S associated with an even number of fennions must be integral, while that for an odd number of them must be half-integral. The resulting composite particles behave collectively like bosons and fennions, respectively, so the wavefunction synnnetry properties associated with bosons can be relevant in chemical physics. One prominent example is the treatment of nuclei, which are typically considered as composite particles rather than interacting protons and neutrons. Nuclei with even atomic number tlierefore behave like individual bosons and those with odd atomic number as fennions, a distinction that plays an important role in rotational spectroscopy of polyatomic molecules. 

Amorphous materials exliibit speeial quantum properties with respeet to their eleetronie states. The loss of periodieify renders Bloeh s theorem invalid k is no longer a good quantum number. In erystals, stnietural features in the refleetivify ean be assoeiated with eritieal points in the joint density of states. Sinee amorphous materials eaimot be deseribed by k-states, seleetion niles assoeiated with k are no longer appropriate. Refleetivify speetra and assoeiated speetra are often featureless, or they may eonespond to highly smoothed versions of the erystalline speetra. 

Each such nonual mode can be assigned a synuuetry in the point group of the molecule. The wavefrmctions for non-degenerate modes have the following simple synuuetry properties the wavefrmctions with an odd vibrational quantum number v. have the same synuuetry as their nonual mode 2the ones with an even v. are totally symmetric. The synuuetry of the total vibrational wavefrmction (Q) is tlien the direct product of the synuuetries of its constituent nonual coordinate frmctions (p, (2,). In particular, the lowest vibrational state. 

The negative sign in equation (b 1.15.26) implies that, unlike the case for electron spins, states with larger magnetic quantum number have smaller energy for g O. In contrast to the g-value in EPR experiments, g is an inlierent property of the nucleus. NMR resonances are not easily detected in paramagnetic systems because of sensitivity problems and increased linewidths caused by the presence of unpaired electron spins. 

The intensities are plotted vs. v, the final vibrational quantum number of the transition. The CSP results (which for this property are almost identical with CI-CSP) are compared with experimental results for h in a low-temperature Ar matrix. The agreement is excellent. Also shown is the comparison with gas-phase, isolated I. The solvent effect on the Raman intensities is clearly very large and qualitative. These show that CSP calculations for short timescales can be extremely useful, although for later times the method breaks down, and CTCSP should be used. 

The trends in chemical and physical properties of the elements described beautifully in the periodic table and the ability of early spectroscopists to fit atomic line spectra by simple mathematical formulas and to interpret atomic electronic states in terms of empirical quantum numbers provide compelling evidence that some relatively simple framework must exist for understanding the electronic structures of all atoms. The great predictive power of the concept of atomic valence further suggests that molecular electronic structure should be understandable in terms of those of the constituent atoms. 

Orbitals are described by specifying their size shape and directional properties Spherically symmetrical ones such as shown m Figure 1 1 are called y orbitals The let ter s IS preceded by the principal quantum number n n = 2 3 etc ) which speci ties the shell and is related to the energy of the orbital An electron m a Is orbital is likely to be found closer to the nucleus is lower m energy and is more strongly held than an electron m a 2s orbital... 

In addition to being negatively charged electrons possess the property of spin The spin quantum number of an electron can have a value of either +5 or According to the Pauli exclusion principle, two electrons may occupy the same orbital only when... 

For atoms, electronic states may be classified and selection rules specified entirely by use of the quantum numbers L, S and J. In diatomic molecules the quantum numbers A, S and Q are not quite sufficient. We must also use one (for heteronuclear) or two (for homonuclear) symmetry properties of the electronic wave function ij/. ... 

In the case of atoms, deriving states from configurations, in the Russell-Saunders approximation (Section 7.1.2.3), simply involved juggling with the available quantum numbers. In diatomic molecules we have seen already that some symmetry properties must be included, in addition to the available quantum numbers, in a discussion of selection rules. 

In the case of atoms (Section 7.1) a sufficient number of quantum numbers is available for us to be able to express electronic selection rules entirely in terms of these quantum numbers. For diatomic molecules (Section 7.2.3) we require, in addition to the quantum numbers available, one or, for homonuclear diatomics, two symmetry properties (-F, — and g, u) of the electronic wave function to obtain selection rules. 

As is to be expected, inherent disorder has an effect on electronic and optical properties of amorphous semiconductors providing for distinct differences between them and the crystalline semiconductors. The inherent disorder provides for localized as well as nonlocalized states within the same band such that a critical energy, can be defined by distinguishing the two types of states (4). At E = E, the mean free path of the electron is on the order of the interatomic distance and the wave function fluctuates randomly such that the quantum number, k, is no longer vaHd. For E < E the wave functions are localized and for E > E they are nonlocalized. For E > E the motion of the electron is diffusive and the extended state mobiHty is approximately 10 cm /sV. For U <, conduction takes place by hopping from one localized site to the next. Hence, at U =, )J. goes through a... 

The nuclei of many isotopes possess an angular momentum, called spin, whose magnitude is described by the spin quantum number / (also called the nuclear spin). This quantity, which is characteristic of the nucleus, may have integral or halfvalues thus / = 0, 5, 1, f,. . . The isotopes C and 0 both have / = 0 hence, they have no magnetic properties. H, C, F, and P are important nuclei having / = 5, whereas and N have / = 1. 

Fermions are particles that have the properties of antisymmetry and a half-integral spin quantum number, among others. 

The arrangement of electrons in an atom is described by means of four quantum numbers which determine the spatial distribution, energy, and other properties, see Appendix 1 (p. 1285). The principal quantum number n defines the general energy level or shell to which the electron belongs. Electrons with n = 1.2, 3, 4., are sometimes referred to as K, L, M, N,. .., electrons. The orbital quantum number / defines both the shape of the electron charge distribution and its orbital angular... 

The fourth quantum number is called the spin angular momentum quantum number for historical reasons. In relativistic (four-dimensional) quantum mechanics this quantum number is associated with the property of symmetry of the wave function and it can take on one of two values designated as -t-i and — j, or simply a and All electrons in atoms can be described by means of these four quantum numbers and, as first enumerated by W. Pauli in his Exclusion Principle (1926), each electron in an atom must have a unique set of the four quantum numbers. 

The fourth quantum number, ms> is associated with electron spin. An electron has magnetic properties that correspond to those of a charged particle spinning on its axis. Either of two spins is possible, clockwise or counterclockwise (Figure 6.5). 

It is not easy to see why the authors believe that the success of orbital calculations should lead one to think that the most profound characterization of the properties of atoms implies such an importance to quantum numbers as they are claiming. As is well known in quantum chemistry, successful mathematical modeling may be achieved via any number of types of basis functions such as plane waves. Similarly, it would be a mistake to infer that the terms characterizing such plane wave expansions are of crucial importance in characterizing the behavior of atoms. 

The integer n labels the wavefunctions and is called a quantum number. In general, a quantum number is an integer (or, in some cases, Section 1.10, a half-integer) that labels a wavefunction, specifies a state, and can be used to calculate the value of a property of the system. For example, we can use n to find an expression for the energy corresponding to each wavefunction. 

LO Name and explain the relation of each of the four quantum numbers to the properties and relative energies of atomic orbitals (Sections 1.8—1.1 1). 

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,... 

In an octahedral crystal field, for example, these electron densities acquire different energies in exactly the same way as do those of the J-orbital densities. We find, therefore, that a free-ion D term splits into T2, and Eg terms in an octahedral environment. The symbols T2, and Eg have the same meanings as t2g and eg, discussed in Section 3.2, except that we use upper-case letters to indicate that, like their parent free-ion D term, they are generally many-electron wavefunctions. Of course we must remember that a term is properly described by both orbital- and spin-quantum numbers. So we more properly conclude that a free-ion term splits into -I- T 2gin octahedral symmetry. Notice that the crystal-field splitting has no effect upon the spin-degeneracy. This is because the crystal field is defined completely by its ordinary (x, y, z) spatial functionality the crystal field has no spin properties. 

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