A1 Vertaisarvioitu alkuperäisartikkeli tieteellisessä lehdessä
Deuteron NMR spin-lattice relaxation of NH3D+ ions in partially deuterated (NH4)(2)SnCl6 and NH4ClO4
Tekijät: Birczynski A, Lalowicz ZT, Szymocha AM, Punkkinen M, Ylinen EE, Vuorimaki AH
Kustantaja: ELSEVIER SCIENCE BV
Julkaisuvuosi: 2006
Lehti:: Chemical Physics
Tietokannassa oleva lehden nimi: CHEMICAL PHYSICS
Lehden akronyymi: CHEM PHYS
Vuosikerta: 327
Numero: 1
Aloitussivu: 119
Lopetussivu: 126
Sivujen määrä: 8
ISSN: 0301-0104
DOI: https://doi.org/10.1016/j.chemphys.2006.04.001
Tiivistelmä
Deuteron spin-lattice relaxation is studied in 5% and 100% deuterated ammonium hexachlorostannate and perchlorate. The relaxation rate is observed to be independent of deuteration down to temperatures slightly lower than that of the maximum. At lower temperatures the rate of the 5% deuterated sample exceeds that of the 100% deuterated sample by four and two orders of magnitude in ammonium hexachlorostannate and perchlorate, respectively. The angular dependence of the deuteron relaxation rate in 5% deuterated ammonium hexachlorostannate at 6 K is explained in terms of existing models on quadrupolar relaxation. In 5% ammonium perchlorate one hydrogen equilibrium position, which lies on the preferred axis for 120 degrees rotations, has a larger probability to be occupied by the deuteron of NH3D+ ions. The deuterons at the other positions are still performing rotational jumps about the preferred C-3 axis and also about the other threefold axes, although at a slower rate. Such observations require a reconsideration of the relaxation process. A somewhat more general expression is derived for the relaxation rate, which agrees with the experimentally observed angular dependence for 5% deuterated ammonium perchlorate at 60 K. At lower temperatures the quadrupole coupling of the deuterons at the preferred axis may become practically time-independent. Then a significant contribution to the relaxation rate can be provided by the deuteron-proton magnetic dipolar interaction, which is still fluctuating fast via the rotation of the three protons about the axis through the stationary deuteron. (C) 2006 Elsevier B.V. All rights reserved.
Deuteron spin-lattice relaxation is studied in 5% and 100% deuterated ammonium hexachlorostannate and perchlorate. The relaxation rate is observed to be independent of deuteration down to temperatures slightly lower than that of the maximum. At lower temperatures the rate of the 5% deuterated sample exceeds that of the 100% deuterated sample by four and two orders of magnitude in ammonium hexachlorostannate and perchlorate, respectively. The angular dependence of the deuteron relaxation rate in 5% deuterated ammonium hexachlorostannate at 6 K is explained in terms of existing models on quadrupolar relaxation. In 5% ammonium perchlorate one hydrogen equilibrium position, which lies on the preferred axis for 120 degrees rotations, has a larger probability to be occupied by the deuteron of NH3D+ ions. The deuterons at the other positions are still performing rotational jumps about the preferred C-3 axis and also about the other threefold axes, although at a slower rate. Such observations require a reconsideration of the relaxation process. A somewhat more general expression is derived for the relaxation rate, which agrees with the experimentally observed angular dependence for 5% deuterated ammonium perchlorate at 60 K. At lower temperatures the quadrupole coupling of the deuterons at the preferred axis may become practically time-independent. Then a significant contribution to the relaxation rate can be provided by the deuteron-proton magnetic dipolar interaction, which is still fluctuating fast via the rotation of the three protons about the axis through the stationary deuteron. (C) 2006 Elsevier B.V. All rights reserved.
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