Reorientational motion of ammonium ions in (NH4)2SO4 and [(NH4)0.16K0.84]2SO4

Goyal, P. S. ; Dasannacharya, B. A. (1978) Reorientational motion of ammonium ions in (NH4)2SO4 and [(NH4)0.16K0.84]2SO4 Journal of Chemical Physics, 68 (5). pp. 2430-2438. ISSN 1674-0068

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We report measurements of quasielastic incoherent neutron scattering from paraelectric (NH4)2SO4 and [(NH4)0.16K0.84]2 SO4 in the temperature range of 227 to 420°K and in the wave vector region of 0.8 to 2.38 Å-1. (NH4)2SO4 has two inequivalent NH+4 ions in a unit cell, labeled I and II, whereas the mixed salt has only one type of NH+4 ion, that is, type II. It is shown that it is possible to get information about the two NH+4 ions separately by combining the data from the two salts. The form factors for the two NH+4 ions and the temperature dependence of the characteristic reorientation time are derived. From the form factors it is shown that for NH+4 (II) ion there is a distribution of characteristic relaxation times for reorientation about the four N-H bonds. On the other hand, for NH+4 (I) ion the reorientation rate about all the four N-H bonds is nearly same. The average characteristic times τI and τII for the two NH+4 ions at room temperature are found to be 12.0±2.0 and 15.8±1.1 psec, respectively. The temperature dependence of τ is very similar for the two salts and can be described by an average description of the type τ=t0expV/kBT with V=1.27±0.17 kcal/mole and τ0=1.65±0.7 psec. The present data are not accurate enough at all temperatures to give separate temperature dependences for τI and τII. The values of τ0 and V are compared with those derived by NMR.

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