Lateral shift absorption

The crystallographic study of the potassium salt is complicated by disorder but in CsOs03N Os=N is 1.676 A and Os=0 1.739-1.741 A. Assignments of the vibrational spectrum of Os03N is assisted by isotopic substitution the higher frequency absorption is shifted significantly on 15N substitution whereas the band just below 900 cm-1 is scarcely affected (Table 1.7) conversely the latter band is shifted by some 50 cm-1 on replacing l60 by l80 [56], Nitrido salts are discussed later (section 1.12.2). 

The EMIRS and SNIFTIRS methods provide the IR vibrational spectra (really the difference spectra - see later) of all species whose population changes either on the electrode surface or in the electrical double layer or in the diffusion layer in response to changing the electrode potential. Spectra will also be obtained for adsorbed species whose population does not change but which undergo a change in orientation or for which the electrode potential alters the Intensity, the position or shape of IR absorption bands. Shifts in band maxima with potential at constant coverage (d nax 6 very common for adsorbed species and they provide valuable information on the nature of adsorbate/absorbent bonding and hence also additional data on adsorbate orientation. 

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