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Selection Rule
In physics and chemistry, a selection rule, or transition rule, formally constrains the possible transitions of a system from one quantum state to another. Selection rules have been derived for electromagnetic transitions in molecules, in atoms, in atomic nuclei, and so on. The selection rules may differ according to the technique used to observe the transition. The selection rule also plays a role in chemical reactions, where some are formally spin-forbidden reactions, that is, reactions where the spin state changes at least once from reactants to products. In the following, mainly atomic and molecular transitions are considered. Overview In quantum mechanics the basis for a spectroscopic selection rule is the value of the ''transition moment integral''  :\int \psi_1^* \, \mu \, \psi_2 \, \mathrm\tau\,, where \psi_1 and \psi_2 are the wave functions of the two states, "state 1" and "state 2", involved in the transition, and is the transition moment operator. Th ...
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Physics
Physics is the natural science that studies matter, its fundamental constituents, its motion and behavior through space and time, and the related entities of energy and force. "Physical science is that department of knowledge which relates to the order of nature, or, in other words, to the regular succession of events." Physics is one of the most fundamental scientific disciplines, with its main goal being to understand how the universe behaves. "Physics is one of the most fundamental of the sciences. Scientists of all disciplines use the ideas of physics, including chemists who study the structure of molecules, paleontologists who try to reconstruct how dinosaurs walked, and climatologists who study how human activities affect the atmosphere and oceans. Physics is also the foundation of all engineering and technology. No engineer could design a flat-screen TV, an interplanetary spacecraft, or even a better mousetrap without first understanding the basic laws of physics ...
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Point Group
In geometry, a point group is a mathematical group of symmetry operations ( isometries in a Euclidean space) that have a fixed point in common. The coordinate origin of the Euclidean space is conventionally taken to be a fixed point, and every point group in dimension ''d'' is then a subgroup of the orthogonal group O(''d''). Point groups are used to describe the symmetries of geometric figures and physical objects such as molecules. Each point group can be represented as sets of orthogonal matrices ''M'' that transform point ''x'' into point ''y'' according to Each element of a point group is either a rotation (determinant of ''M'' = 1), or it is a reflection or improper rotation (determinant of ''M'' = −1). The geometric symmetries of crystals are described by space groups, which allow translations and contain point groups as subgroups. Discrete point groups in more than one dimension come in infinite families, but from the crystallographic restriction theore ...
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Spin Quantum Number
In atomic physics, the spin quantum number is a quantum number (designated ) which describes the intrinsic angular momentum (or spin angular momentum, or simply spin) of an electron or other particle. The phrase was originally used to describe the fourth of a set of quantum numbers (the principal quantum number , the azimuthal quantum number , the magnetic quantum number , and the spin quantum number ), which completely describe the quantum state of an electron in an atom. The name comes from a physical spinning of the electron about an axis, as proposed by Uhlenbeck and Goudsmit. The value of is the component of spin angular momentum parallel to a given direction (the –axis), which can be either +1/2 or –1/2 (in units of the reduced Planck constant). However this simplistic picture was quickly realized to be physically impossible because it would require the electrons to rotate faster than the speed of light. It was therefore replaced by a more abstract quantum-me ...
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Parity (physics)
In physics, a parity transformation (also called parity inversion) is the flip in the sign of ''one'' spatial coordinate. In three dimensions, it can also refer to the simultaneous flip in the sign of all three spatial coordinates (a point reflection): :\mathbf: \beginx\\y\\z\end \mapsto \begin-x\\-y\\-z\end. It can also be thought of as a test for chirality of a physical phenomenon, in that a parity inversion transforms a phenomenon into its mirror image. All fundamental interactions of elementary particles, with the exception of the weak interaction, are symmetric under parity. The weak interaction is chiral and thus provides a means for probing chirality in physics. In interactions that are symmetric under parity, such as electromagnetism in atomic and molecular physics, parity serves as a powerful controlling principle underlying quantum transitions. A matrix representation of P (in any number of dimensions) has determinant equal to −1, and hence is distinct from a rotati ...
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Spin (physics)
Spin is a conserved quantity carried by elementary particles, and thus by composite particles ( hadrons) and atomic nuclei. Spin is one of two types of angular momentum in quantum mechanics, the other being ''orbital angular momentum''. The orbital angular momentum operator is the quantum-mechanical counterpart to the classical angular momentum of orbital revolution and appears when there is periodic structure to its wavefunction as the angle varies. For photons, spin is the quantum-mechanical counterpart of the polarization of light; for electrons, the spin has no classical counterpart. The existence of electron spin angular momentum is inferred from experiments, such as the Stern–Gerlach experiment, in which silver atoms were observed to possess two possible discrete angular momenta despite having no orbital angular momentum. The existence of the electron spin can also be inferred theoretically from the spin–statistics theorem and from the Pauli exclusion principle— ...
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Electric Dipole Transition
An electric dipole transition is the dominant effect of an interaction of an electron in an atom with the electromagnetic field. Following reference, consider an electron in an atom with quantum Hamiltonian H_0 , interacting with a plane electromagnetic wave : (,t)=E_0 \cos(ky-\omega t), \ \ \ (,t)=B_0 \cos(ky-\omega t). Write the Hamiltonian of the electron in this electromagnetic field as : H(t) \ = \ H_0 + W(t). Treating this system by means of time-dependent perturbation theory, one finds that the most likely transitions of the electron from one state to the other occur due to the summand of W(t) written as : W_\mathrm(t) = \frac p_z \sin \omega t. \, Electric dipole transitions are the transitions between energy levels in the system with the Hamiltonian H_0 + W_\mathrm(t) . Between certain electron states the electric dipole transition rate may be zero due to one or more selection rules, particularly the angular momentum selection rule. In such a case, the ...
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Atomic Orbitals
In atomic theory and quantum mechanics, an atomic orbital is a function describing the location and wave-like behavior of an electron in an atom. This function can be used to calculate the probability of finding any electron of an atom in any specific region around the atom's nucleus. The term ''atomic orbital'' may also refer to the physical region or space where the electron can be calculated to be present, as predicted by the particular mathematical form of the orbital. Each orbital in an atom is characterized by a set of values of the three quantum numbers , , and , which respectively correspond to the electron's energy, angular momentum, and an angular momentum vector component ( magnetic quantum number). Alternative to the magnetic quantum number, the orbitals are often labeled by the associated harmonic polynomials (e.g., ''xy'', ). Each such orbital can be occupied by a maximum of two electrons, each with its own projection of spin m_s. The simple names s orbital, p o ...
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Centrosymmetric
In crystallography, a centrosymmetric point group contains an inversion center as one of its symmetry elements. In such a point group, for every point (x, y, z) in the unit cell there is an indistinguishable point (-x, -y, -z). Such point groups are also said to have ''inversion'' symmetry. Point reflection is a similar term used in geometry. Crystals with an inversion center cannot display certain properties, such as the piezoelectric effect. The following space groups have inversion symmetry: the triclinic space group 2, the monoclinic 10-15, the orthorhombic 47-74, the tetragonal 83-88 and 123-142, the trigonal 147, 148 and 162-167, the hexagonal 175, 176 and 191-194, the cubic 200-206 and 221-230. Point groups lacking an inversion center (non-centrosymmetric) can be '' polar'', ''chiral'', both, or neither. A '' polar'' point group is one whose symmetry operations leave more than one common point unmoved. A polar point group has no unique origin because each of those un ...
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Laporte Rule
The Laporte rule is a rule that explains the intensities of absorption spectra for chemical species. It is a selection rule that rigorously applies to chromophores that are centrosymmetric, i.e. with an inversion centre. It states that electronic transitions that conserve parity are forbidden. Thus transitions between states that are symmetric with respect to an inversion centre will not be observed. Transitions between states that are unsymmetric with respect to inversion are forbidden as well. In the language of symmetry, ''g'' (gerade = even (German)) → ''g'' and ''u'' (ungerade = odd) → ''u'' transitions are forbidden. Allowed transitions in such molecules must involve a change in parity, either ''g'' → ''u'' or ''u'' → ''g''. The Laporte rule stipulates that s to s, p to p, d to d, etc. transitions should not be observed in centrosymmetric compounds. Practically speaking, only d-d transitions occur in the visible region of the spectrum. Thus, the Laporte rule is most ...
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Cambridge University Press
Cambridge University Press is the university press of the University of Cambridge. Granted letters patent by Henry VIII of England, King Henry VIII in 1534, it is the oldest university press in the world. It is also the King's Printer. Cambridge University Press is a department of the University of Cambridge and is both an academic and educational publisher. It became part of Cambridge University Press & Assessment, following a merger with Cambridge Assessment in 2021. With a global sales presence, publishing hubs, and offices in more than 40 Country, countries, it publishes over 50,000 titles by authors from over 100 countries. Its publishing includes more than 380 academic journals, monographs, reference works, school and university textbooks, and English language teaching and learning publications. It also publishes Bibles, runs a bookshop in Cambridge, sells through Amazon, and has a conference venues business in Cambridge at the Pitt Building and the Sir Geoffrey Cass Spo ...
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Character Tables
In group theory, a branch of abstract algebra, a character table is a two-dimensional table whose rows correspond to irreducible representations, and whose columns correspond to conjugacy classes of group elements. The entries consist of characters, the traces of the matrices representing group elements of the column's class in the given row's group representation. In chemistry, crystallography, and spectroscopy, character tables of point groups are used to classify ''e.g.'' molecular vibrations according to their symmetry, and to predict whether a transition between two states is forbidden for symmetry reasons. Many university level textbooks on physical chemistry, quantum chemistry, spectroscopy and inorganic chemistry devote a chapter to the use of symmetry group character tables. Definition and example The irreducible complex characters of a finite group form a character table which encodes much useful information about the group ''G'' in a compact form. Each row is labe ...
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Even And Odd Functions
In mathematics, even functions and odd functions are functions which satisfy particular symmetry relations, with respect to taking additive inverses. They are important in many areas of mathematical analysis, especially the theory of power series and Fourier series. They are named for the parity of the powers of the power functions which satisfy each condition: the function f(x) = x^n is an even function if ''n'' is an even integer, and it is an odd function if ''n'' is an odd integer. Definition and examples Evenness and oddness are generally considered for real functions, that is real-valued functions of a real variable. However, the concepts may be more generally defined for functions whose domain and codomain both have a notion of additive inverse. This includes abelian groups, all rings, all fields, and all vector spaces. Thus, for example, a real function could be odd or even (or neither), as could a complex-valued function of a vector variable, and so on. The gi ...
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