A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Spin-lattice relaxation in ammonium compounds with a complex molecular dynamics
Tekijät: Lalowicz ZT, Punkkinen M, Vuorimaki AH, Ylinen EE, Detken A, Ingman LP
Kustantaja: ELSEVIER SCIENCE BV
Julkaisuvuosi: 1997
Lehti:: Solid State Nuclear Magnetic Resonance
Tietokannassa oleva lehden nimi: SOLID STATE NUCLEAR MAGNETIC RESONANCE
Lehden akronyymi: SOLID STATE NUCL MAG
Vuosikerta: 8
Numero: 2
Aloitussivu: 89
Lopetussivu: 107
Sivujen määrä: 19
ISSN: 0926-2040
DOI: https://doi.org/10.1016/S0926-2040(96)01288-X
Tiivistelmä
Expressions are derived for the initial relaxation rate 1/T-1 of protons and deuterons of nontunnelling NH4 and ND4 groups reorienting about various symmetry axes in solids. The reorientation rates are modified by a trigonal, tetragonal or monoclinic distortion of the predominantly cubic hindering potential. When the rates differ sufficiently from each other, two T-1 minima are observed with a characteristic ratio. Experiments were performed in NH4VO3, (NH4)(2)S2O8, (NH4)(2)PtCl4, and their deuterated modifications, which all exhibit two T-1 minima. In NH4VO3 and ND4VO3 the relaxation and spectral data agree rather well with the model of trigonal distortion. Also (NH4)(2)S2O8 has a preferred threefold axis but there, the large tunnel splitting of protons has to be taken into account before an agreement is reached. All the purely reorientational models fail with (NH4)(2)PtCl4, where, instead, the ammonium groups are proposed to be ordered into domains at low temperatures. The groups inside the domains and boundary regions give rise to the high- and low-temperature T-1 minima, respectively. The boundaries are also believed to give rise to the narrow component in the deuteron spectrum at low temperatures. Evidence for a proton tunnelling frequency of 32 MHz is found in (NH4)(2)PtCl4. (C) 1997 Elsevier Science B.V.
Expressions are derived for the initial relaxation rate 1/T-1 of protons and deuterons of nontunnelling NH4 and ND4 groups reorienting about various symmetry axes in solids. The reorientation rates are modified by a trigonal, tetragonal or monoclinic distortion of the predominantly cubic hindering potential. When the rates differ sufficiently from each other, two T-1 minima are observed with a characteristic ratio. Experiments were performed in NH4VO3, (NH4)(2)S2O8, (NH4)(2)PtCl4, and their deuterated modifications, which all exhibit two T-1 minima. In NH4VO3 and ND4VO3 the relaxation and spectral data agree rather well with the model of trigonal distortion. Also (NH4)(2)S2O8 has a preferred threefold axis but there, the large tunnel splitting of protons has to be taken into account before an agreement is reached. All the purely reorientational models fail with (NH4)(2)PtCl4, where, instead, the ammonium groups are proposed to be ordered into domains at low temperatures. The groups inside the domains and boundary regions give rise to the high- and low-temperature T-1 minima, respectively. The boundaries are also believed to give rise to the narrow component in the deuteron spectrum at low temperatures. Evidence for a proton tunnelling frequency of 32 MHz is found in (NH4)(2)PtCl4. (C) 1997 Elsevier Science B.V.
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