Vibrational spectra halides

Ethylenediamine complexes Extraction Halide complexes structures vibrational spectra Halides +3 state +4 state +5 state +6 state... 

By measurement of the wave length of the residual rays, for instance with a diffraction grating, it is possible to get a direct measurement of the maximum frequency in the optical band of the vibration spectrum of an alkali halide. If we treat the spectrum by the Debye method, regarding... 

This criterion, and the presence of an additional intense band well below 3,000 cm i, point to hydrogen bonding in pyridinium nitrate, bifluoride, methanesulphonate and the halides. Fairly complete assignments have been made for the pyridinium ion vibrational spectrum, that of the N-deuterated form and of l-methylpyridinium oa. Data for a number of monosubstituted pyridines and their cations are also available . ... 

Infrared spectroscopy is not as inherently informative with regard to metal interactions in highly symmetrical metal-metal bound dimers as is Raman spectroscopy, since the totally symmetric metal-metal stretch is a forbidden absorption in the infrared experiment. Oldham and Ketteringham have prepared mixed-halide dimers of the type Re2ClxBr 2xto lower the symmetry and hence introduce some infrared allowedness into the Re-Re stretching mode (206). Indeed, the appearance of a medium-intensity band at 274 cm 1 in the infrared spectrum of the mixed-halo species was considered to be the result of absorption by the metal—metal stretching vibration, which was also observed in the Raman spectrum at 274 cm ". ... 

Substituted NH ions Whalley, 28> discussed the spectroscopic effects of orientional disorder about one axis (in contrast to the disorder about three axes as described by Whalley and Bertie 03) and Bertie and Whalley 129> in the a-phases of the methylammonium halides. In principle, all vibrations of an orientational disordered crystal are spectroscopically active, but if the disorder is only about one axis, some restrictions operate, the symmetric bands are sharp in the one-dimensional disordered case, but the bands due to asymmetric vibrations (E) are broad. Whalley use the infra-red results of Sandorfy et al. 130>131> 0f the CH3 -ammonium halides to illustrate the effect which is predicted from interionic coupling of the E-modes. No such effect is visible in the spectrum of the methoxyammonium ion CH3ONH3 reported by Nelson, 32>. 

In this case, as with all other hydrogen halide lasers, only P branch transitions are observed, indicating that only partial inversion is attained. The vibrational transitions observed are 1 - 0 and 2 -+ 1. There is a definite threshold flash energy, below which no laser action is observed because the chain decomposition is not fast enough. The development in time of the emission spectrum was observed and discussed in terms of rotational relaxation. 

The pellet (pressed-disk) technique depends on the fact that dry, powdered potassium bromide (or other alkali metal halides) can be compacted under pressure to form transparent disks. The sample (0.5-1.0 mg) is intimately mixed with approximately 100 mg of dry, powdered KBr. Mixing can be effected by thorough grinding in a smooth agate mortar or, more efficiently, with a small vibrating ball mill, or by lyophilization. The mixture is pressed with special dies under a pressure of 10,000-15,000 psi into a transparent disk. The quality of the spectrum depends on the intimacy of mixing and the reduction of the suspended particles to 2 gm or less. Microdisks, 0.5-1.5 mm in diameter, can be used with a beam condenser. The microdisk technique permits examination of samples as small as 1 fxg. Bands near 3448 and 1639 cm-1, resulting from moisture, frequently appear in spectra obtained by the pressed-disk technique. 

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