Infrared and Raman spectra of magnesium ammonium phosphate hexahydrate (struvite) and its isomorphous analogues. V. Spectra of protiated and partially deuterated magnesium ammonium arsenate hexahydrate (arsenstruvite)

Add time:08/10/2019    Source:sciencedirect.com

The Fourier transform infrared and Raman spectra of magnesium ammonium arsenate hexahydrate, MgNH4AsO4 · 6H2O (arsenstruvite) and of its deuterated analogues were recorded at room temperature (RT) and the boiling temperature of liquid nitrogen (LNT). Not surprisingly, the spectra show pronounced similarities with the corresponding spectra of the previously studied magnesium potassium phosphate hexahydrate and magnesium ammonium phosphate hexahydrate with the expected differences in the regions of the arsenate vibrations. The main contribution to the intensity of the complex feature in the X–H stretching region (X being O or N) comes from the stretching vibrations of the water molecules, whereas the vibrations of the ammonium ions are less important as long as the intensity is concerned. This is due not only to the fact that four crystallographically different water molecules of crystallization exist in the structure (as compared with a single type of ammonium ions) but also because the hydrogen bonds formed by the water molecules are much stronger than those in which the ammonium ions take part. Difference infrared spectra were obtained by subtracting the properly normalized spectrum of the protiated compound from the spectrum of a deuterated analogue with low deuterium content. As evidenced by the spectra of the partially deuterated analogues and by the difference spectra, vibrational interactions are present in the crystal. Probably the most dramatic is the result of such an interaction producing a deep Evans-type hole in the stretching region of the difference spectrum but additional cases of vibrational mixing are found in the low-frequency region.

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