Charge transfer intensity

The intensity associated with charge-transfer excitation of an electron from these filled ligand orbitals into the half-occupied Cu dx2.y2 orbital also reflects metal-ligand bonding. Charge-transfer intensity is proportional to (RS)2, where S is the overlap of the donor and acceptor... 

Although the T1 center of green AcNiR exhibits the classic coordination sphere of a T1 site with an axial S(Met), the distortion of the site weakens the Cu—S(Cys) bond, as demonstrated by spectral features with a decrease in the dominant S(Cys)7i Cu(II) charge-transfer intensity together with a more significant S(Cys)a Cu(II) intensity that causes increased absorption around 450 nm changing the color from blue to green (92). 

Bhowrmk, B.B. (1971) Solvent effect on the charge transfer intensity of benzene-iodine complex. Spectrochim. Acta, Part A, 27 A, 321—327. 

Krishna, V.G. and Bhowmik, B.B. (1968) Charge transfer intensities of iodine complexes with yV-heterocyclics. J. Am. Chem. Soc., 90,1700-1705. 

The Franck-Condon principle reflected in tire connection between optical and tliennal ET also relates to tire participation of high-frequency vibrational degrees of freedom. Charge transfer and resonance Raman intensity bandshape analysis has been used to detennine effective vibrational and solvation parameters [42,43]. 

Intense sodium D-line emission results from excited sodium atoms produced in a highly exothermic step (175). Many gas-phase reactions of the alkafl metals are chemiluminescent, in part because their low ioni2ation potentials favor electron transfer to produce intermediate charge-transfer complexes such as [Ck Na 2] (1 )- There appears to be an analogy with solution-phase electron-transfer chemiluminescence in such reactions. 

In view of the magnitude of crystal-field effects it is not surprising that the spectra of actinide ions are sensitive to the latter s environment and, in contrast to the lanthanides, may change drastically from one compound to another. Unfortunately, because of the complexity of the spectra and the low symmetry of many of the complexes, spectra are not easily used as a means of deducing stereochemistry except when used as fingerprints for comparison with spectra of previously characterized compounds. However, the dependence on ligand concentration of the positions and intensities, especially of the charge-transfer bands, can profitably be used to estimate stability constants. 

The electrodeposition of Ag has also been intensively investigated [41 3]. In the chloroaluminates - as in the case of Cu - it is only deposited from acidic solutions. The deposition occurs in one step from Ag(I). On glassy carbon and tungsten, three-dimensional nucleation was reported [41]. Quite recently it was reported that Ag can also be deposited in a one-electron step from tetrafluoroborate ionic liquids [43]. However, the charge-transfer reaction seems to play an important role in this medium and the deposition is not as reversible as in the chloroaluminate systems. 

Many complexes of metals with organic ligands absorb in the visible part of the spectrum and are important in quantitative analysis. The colours arise from (i) d- d transitions within the metal ion (these usually produce absorptions of low intensity) and (ii) n->n and n n transitions within the ligand. Another type of transition referred to as charge-transfer may also be operative in which an electron is transferred between an orbital in the ligand and an unfilled orbital of the metal or vice versa. These give rise to more intense absorption bands which are of analytical importance. 

The mixed-valence ion has an intervalence charge transfer band at 1562nm not present in the spectra of the +4 and +6 ions. Similar ions have been isolated with other bridging ligands, the choice of which has a big effect on the position and intensity of the charge-transfer band (e.g. L = bipy, 830 nm). 

These iridium(IV) complexes have UV-visible spectra dominated by intense absorptions around 500 nm (X = Cl) and 700 nm (X = Br) assignable to 7tx —> Ir(t2g) ligand-to-metal charge-transfer bonds. 

FIGURE 16.33 In a ligand-to-metal charge-transfer transition, an energetically excited electron migrates from a ligand to the central metal ion. This type of transition is responsible for the intense purple of the permanganate ion, MnCF,. ... 

The colors that we have described arise from d-d transitions, in which an electron is excited from one d-orbital into another. In a charge-transfer transition an electron is excited from a ligand onto the metal atom or vice versa. Charge-transfer transitions are often very intense and are the most common cause of the familiar colors of d-metal complexes, such as the transition responsible for the deep purple of permanganate ions, Mn04 (Fig. 16.33). 

Hence, reactions which proceed via complex formation or stripping reactions involving transfer of a relatively massive moiety either are not observed or are registered at grossly distorted intensities. An additional complication is that elastic or nonreactive scattering collisions may allow a primary ion to be detected as a secondary ion. Simple charge transfer... 

It is particularly difficult to study charge transfer reactions by the usual internal ionization method since the secondary ions produced will always coincide with ions produced in primary ionization processes. Indeed these primary ions frequently constitute the major fraction of the total ion current, and the small intensity changes originating from charge transfer reactions are difficult to detect. For example, Field and Franklin (5) were unable to detect any charge transfer between Xe + and CH4 by the internal ionization method although such reactions have been observed using other techniques (3, 9,22). 

The C2 ion intensities are of course not primary charge transfer abundances but correspond approximately to relative steady-state... 

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