论文标题

Natisi2O6中的轨道障碍和订购:29SI和23NA NMR研究

Orbital disorder and ordering in NaTiSi2O6: 29Si and 23Na NMR Study

论文作者

Heinmaa, Ivo, Rästa, Riho, Silverstein, Harlyn J., Wiebe, Christopher R., Stern, Raivo

论文摘要

Natisi2O6是一种示例化合物,显示了TC = 210 K处的轨道辅助自旋 - 旋转相变。我们介绍了Natisi2O6的29SI和23NA NMR测量结果。魔术角旋转技术的使用明确表明,在t> tc上只能看到一个动态平均的硅位点。在冷却时,29SI MAS NMR频谱显示出有趣的变化。在TC下方,频谱变得非常宽。进一步冷却,它显示了两条不平等强度的宽线,随着温度降低,它们变得更窄。在70 K以下,两个狭窄的线的化学位移是dimagnetic Silicates典型的化学位移。两个位点的超细场值为7.4 KOE/KB和4.9 KOE/KB。在高温下的顺磁性状态下,发现29SI的自旋晶格松弛依赖于温度弱。在TC以下的Arrhenius类型温度依赖性的弛豫率依赖性表示能量间隙D/kb = 1000(50)K。在温度区域从120到300 K的温度区域中,松弛速率的频率很强。在室温下,我们发现功率定律依赖于-0.65(5)的Larmor频率。对于70 <t <120 k,松弛似乎是非指数的,我们由于固定的顺磁中心而分配给弛豫。磁化恢复曲线的模拟显示这些中心浓度与磁敏感性成正比的温度依赖性。 23NA的NMR光谱显示了典型形状的双核中心过渡的线。 23NA共振的较小频移对应于0.32 KOE/KB的非常小的高精细场。此外,在T> TC处,23NA频谱显示了另一个Lorentzian形状的共振,我们将其归因于Na位点,其中四极管耦合部分通过离子运动平均。

NaTiSi2O6 is an exemplary compound, showing an orbital assisted spin-Peierls phase transition at Tc = 210 K. We present the results of 29Si and 23Na NMR measurements of NaTiSi2O6. The use of magic angle spinning techniques unambiguously shows that only one dynamically averaged silicon site can be seen at T > Tc. At cooling, the 29Si MAS NMR spectrum shows interesting changes. Immediately below Tc the spectrum gets very broad. Cooling further, it shows two broad lines of unequal intensities which become narrower as the temperature decreases. Below 70 K two narrow lines have chemical shifts that are typical for diamagnetic silicates. The hyperfine field values for the two sites are 7.4 kOe/kB and 4.9 kOe/kB. In the paramagnetic state at high temperature, the spin-lattice relaxation of 29Si was found to be weakly temperature dependent. Below Tc the Arrhenius type temperature dependence of the relaxation rate indicates an energy gap D/kB = 1000(50) K. In the temperature region from 120 to 300 K the relaxation rate was strongly frequency dependent. At room temperature we found a power law dependence on Larmor frequency of -0.65(5). For 70 < T < 120 K the relaxation appeared to be non-exponential which we assigned to a relaxation due to fixed paramagnetic centers. Simulation of the magnetization recovery curve showed a temperature dependence of the concentration of these centers proportional to the magnetic susceptibility. The NMR spectrum of 23Na shows the line with typical shape for the central transition of a quadrupolar nucleus. A small frequency shift of 23Na resonance corresponds to a very small hyperfine field of 0.32 kOe/kB . In addition, at T > Tc the 23Na spectrum shows another Lorentzian shaped resonance which we attribute to the Na sites where the quadrupolar coupling is partly averaged out by ionic motion.

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