Crystal band splitting

Instead, we believe the electronic structure changes are a collective effect of several distinct processes. For example, at surfaces the loss of the bulk symmetry will induce electronic states with different DOS compared to bulk. As the particle sizes are decreased, the contribution of these surface related states becomes more prominent. On the other hand, the decrease of the coordination number is expected to diminish the d-d and s-d hybridization and the crystal field splitting, therefore leading to narrowing of the valence d-band. At the same time, bond length contraction (i.e. a kind of reconstruction ), which was observed in small particles [89-92], should increase the overlap of the d-orbitals of the neighboring atoms, partially restoring the width of the d-band. 

Table 2. Absorption bands, crystal-field splitting and centre of gravity of the Sd level of Eu2+ in several host lattices all values in kK)...

Host lattice Coordination Eu2+ ion Absorption bands Crystal field splitting Centre 54 level Ref. 

Electron configuration of Bp" is (6s) (6p) yielding a Pip ground state and a crystal field split Pap excited state (Hamstra et al. 1994). Because the emission is a 6p inter-configurational transition Pap- Pip. which is confirmed by the yellow excitation band presence, it is formally parity forbidden. Since the uneven crystal-field terms mix with the (65) (75) Si/2 and the Pap and Pip states, the parity selection rule becomes partly lifted. The excitation transition -Pl/2- S 1/2 is the allowed one and it demands photons with higher energy. 

Figure 4.37a represents the time-resolved luminescence spectrum of a hydrozincite under 266 nm laser excitation. A relatively broad band is detected at 430 nm, which is responsible for the well-known blue hydrozindte luminescence. Its spectral position and decay time of approximately 700 ns are typical for Eu luminescence. However, the excitation spectrum of this band consists of one narrow band at 240 nm (Fig. 4.37b), which does not correspond to an Eu " excitation spectrum. Two bands usually characterize the latter with relatively small Stokes shifts of 30-50 nm caused by crystal field splitting of the 4/ 5d-levels. Moreover, the measured Eu concentrations in the hydrozincite samples under investigation are very low (less than 0.5 ppm) and they do not correlate with the intensity of the blue luminescence, i.e. the band at 430 nm. 

In open shell metals, these empty states can be d- or f-states somewhat hybridized with band states (see Chap. A). In a metal, these states may be pulled down into the conduction band (as a virtual state, see Chap. A) in a compound, presenting a ligand valence band (insulator or semiconductor), they may be pulled down to an energy position coinciding with or very near to this valence band (as a true impurity level). The two possible final states (Eqs. 22 a and 22 b) explain the occurrence of a split response one of the crystal band electrons occupies either the outer hole level P (Eq. 22 a) or the more bandlike hole B " (Eq. 22 b). 

Crystallinity In crystallization of polymers, the polymer forms crystalline and amorphous regions [2,4,25]. The formation of crystalline regions is accompanied by an increase in new vibrational modes caused by their crystal lattice interactions [2]. The IR spectrum of a given polymer differs by various absorption bands, depending on whether it is in the amorphous or crystalline state [2]. The IR spectrum exhibits regularity bands, splitting, and frequency shifts. Other absorption bands are not affected by crystallization and remain the same in both cases. Crystalline and amorphous bands can be used in the determination of the degree of crystallinity independent bands are useful for the determination of sample thickness [2],... 

Fig. 1.6 Plot against k of energies of five d-bands when the bandwidths are greater than the crystal-field splitting, so that hybridization takes place between the xy and x2—y2...

It is conjectured that in those materials in which the t2g band (separated from the eg band by crystal-field splitting) is not full, the carriers lie in this band the gap is that needed to form from two Mn2+, a Mn3+ and a Mn+ ion, for instance. 

More recently it has been found15 that a correlation exists between spectroscopic parameters of the divalent aqua ions of the metals Cr to Ni, and the polarographic y2. A linear relationship was found between A0 and crystal field splitting parameter, ot the transfer coefficient, n the number of electrons transferred in the reduction, EVl the polarographic half-wave potential and E° the standard electrode potential. The use of the crystal field splitting parameter would seem to be a more sensible parameter to use than the position of Amax for the main absorption band as the measured Amax may not be a true estimate of the relevant electronic transition. This arises because the symmetry of the complex is less than octahedral so that the main absorption band in octahedral symmetry is split into at least two components with the result that... 

The [Ti(NCS)g]3- ion exhibits a single absorption band at 544 nm. Calculate the crystal field splitting energy A (in kj/mol). Is NCS- a stronger or weaker field ligand than water Predict the color of [Ti(NCS)6]3-. 

Effects of lattice relaxation The overall spectral features are reproduced without any empirical parameters except for the fine structures around peaks C, D, E. However, the separation of the bands is somewhat overestimated. One of the reasons for this overestimation is ignorance of the lattice relaxation effects due to the substitution of Ce3+ for Y3+. Combes et al. (1997) suggested that the origin of the peaks C, D is a crystal field splitting due to the lowering of the symmetry originating from the substitution of Ce3+ for Y3+. 

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