Scheuermann M, Geil B, Löw F, Fujara F
Institut fur Festkorperphysik, TU Darmstadt, Hochschulstr. 6, 64289 Darmstadt, Germany.
J Chem Phys. 2009 Jan 14;130(2):024506. doi: 10.1063/1.3047789.
(2)H NMR spectra, spin-lattice relaxation, and stimulated echoes have been measured in polycrystalline ice II in the temperature range of 84-145 K at ambient pressure. From the spectra we obtain the quadrupole coupling constant in ice II, e(2)qQ/h = (225.7+/-1.2) kHz, and the asymmetry parameter, eta = 0.118+/-0.006. At 145 K, a phase transition of ice II into ice I(c) is observed by a change of both, its spectral and relaxation behavior. The spin-lattice relaxation in ice II is bimodal, showing two components of approximately the same weight. The fast relaxing part of the recovery curve progresses monoexponentially and the temperature dependence of its mean relaxation time corresponds to an unusually low activation energy of 2.3 kJ mol(-1). The slowly relaxing part, displaying average relaxation times of about 4000 s, is significantly stretched with a Kohlrausch parameter of 0.6 and shows no temperature dependence. The stimulated echo experiments show a temperature independent correlation decay. The analysis of intermediate states indicates that no small-angle motions are involved in the underlying process. Both findings exclude an interpretation in terms of molecular motion. Instead, spin diffusion in the deuteron system has to be considered as the origin of the phenomena observed in the stimulated echo experiments.
在环境压力下,于84 - 145K温度范围内对多晶冰II进行了(2)H核磁共振谱、自旋晶格弛豫和受激回波测量。从谱图中我们得到冰II中的四极耦合常数,e(2)qQ/h = (225.7±1.2) kHz,以及不对称参数,η = 0.118±0.006。在145K时,通过其光谱和弛豫行为的变化观察到冰II向冰I(c)的相变。冰II中的自旋晶格弛豫是双峰的,显示出两个权重近似相同的分量。恢复曲线中快速弛豫部分呈单指数进展,其平均弛豫时间的温度依赖性对应于异常低的2.3 kJ mol(-1)的活化能。缓慢弛豫部分显示平均弛豫时间约为4000 s,具有显著的伸展性,Kohlrausch参数为0.6,且无温度依赖性。受激回波实验显示出与温度无关的相关衰减。中间态分析表明,潜在过程中不涉及小角度运动。这两个发现都排除了基于分子运动的解释。相反,必须将氘核系统中的自旋扩散视为受激回波实验中观察到的现象的起源。