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Laporte forbidden transition

To the writer s knowledge, it has not been pointed out that moderate deviations from the highest symmetry available to the chromophore, producing comparatively high intensities of Laporte-forbidden transitions and a variety of observable effects, are characteristic for soft central atoms. At an instantaneous picture, Cu(H20) 2 and other instances of Cu(II)06 are not cubic, i.e. having three equivalent Cartesian axes. [Pg.25]

Table 1. Wave-numbers o (in the unit 1000 cm-1) and oscillator strengths P (in the unit 10—S) of spin-allowed (but Laporte-forbidden) transitions in nickel(II), copper(II) and palladium(II) complexes of water, ammonia, ethylenediamine (en), diethylenetriamine (den) and pyridine (py). Shoulders in parentheses... Table 1. Wave-numbers o (in the unit 1000 cm-1) and oscillator strengths P (in the unit 10—S) of spin-allowed (but Laporte-forbidden) transitions in nickel(II), copper(II) and palladium(II) complexes of water, ammonia, ethylenediamine (en), diethylenetriamine (den) and pyridine (py). Shoulders in parentheses...
The dipole moment operator ( x) has associated with it ungerade character so the integral will be zero if v i[ and v g are both either gerade or ungerade. Again, Laporte-forbidden transitions do occur (with 10 -10 the intensity of fully allowed transitions) because of mixing of the orbitals in the excited state in noncentrosymmetric sites, and even in centrosym-metric sites as a result of vibrations of the metal atoms away from the center of symmetry (vibronic coupling). [Pg.41]

In the transition group complexes containing a partly filled d shell, it is possible that a reminiscent Gillespie-effect contributes to the intensity of Laporte-forbidden transitions. Thus, the absorption band of Co(NH3)6 has roughly the same oscillator strength as -that of Co(NH3)5C1+2, and there is some evidence (54) that Cu is above the plane of the four ammonia molecules, not only in the tetragonal-pyramidic Cu(NH3)5+2, but also in an instantaneous picture in Cu(NH3)4 2 which would constitute essentially a Gillespie effect. [Pg.167]

Lanthanide compounds have attracted attention due to their potential applications as various materials. Their intra-4f electronic transition, the so-called f-f transition, is one of the most discriminative properties and used extensively for many optics, such as lasers, fibers, optical displays, and biosensors [1-3]. The probability of photo absorption is represented by oscillator strength, a dimensionless quantity. The oscillator strengths of f-f transitions are small, typically in the order of 10 , reflecting Laporte forbidden transitions, and their absorption and emission spectra have sharp peaks in visible, near infrared, and near ultraviolet regions. Despite the usefulness of these systems, there are only a few relevant ab initio studies of the f-f transition intensities that explicitly included ligand electrons [4—7] because these calculations are difficult due to the importance of both relativistic and electron correlation effects. [Pg.214]


See other pages where Laporte forbidden transition is mentioned: [Pg.189]    [Pg.445]    [Pg.26]    [Pg.32]    [Pg.4]    [Pg.6]    [Pg.67]    [Pg.67]    [Pg.40]    [Pg.73]    [Pg.167]    [Pg.445]    [Pg.37]    [Pg.37]    [Pg.899]    [Pg.445]    [Pg.117]    [Pg.127]    [Pg.161]    [Pg.1036]    [Pg.242]    [Pg.68]    [Pg.1152]    [Pg.138]    [Pg.318]    [Pg.119]   
See also in sourсe #XX -- [ Pg.4 , Pg.8 ]

See also in sourсe #XX -- [ Pg.445 ]

See also in sourсe #XX -- [ Pg.445 ]




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Laporte-forbidden ligand-field transitions

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