Decressain R, Carpentier L, Cochin E, Descamps M
Laboratoire de Dynamique et Structure des Matériaux Moléculaires, U.M.R. CNRS 8024, Bât. P5, Ust Lille, 59655 Villeneuve d'Ascq, France.
J Chem Phys. 2005 Jan 15;122(3):34507. doi: 10.1063/1.1827213.
The dynamic properties of plastic crystalline mixed adamantane's derivatives namely cyanoadamantane (75%) and chloroadamantane (25%) were investigated by dielectric and nuclear magnetic resonance (NMR) spectroscopy, covering a spectral range of 12 decades in the temperature range 110-420 K. Phase transformations were studied and dynamical parameters of the plastic (I), glassy (Ig), and ordered (III) phases were determined and compared with those of pure compounds. The dynamics of the supercooled plastic phase is characterized by an alpha-process exhibiting an Arrhenius behavior which classified the mixed compound as a strong glass former. In the plastic phase, NMR relaxation times were interpreted by using a Frenkel model, which takes into account structural equilibrium positions. This model explains adequately the experimental results by considering two molecular motions. In both the glassy state and plastic phase the motional parameters agree with those of 1-cyanoadamantane. On the contrary, in the ordered phase, the motional parameters related to the uniaxial rotation of chloroadamantane molecules indicate an accelerated motion.
通过介电和核磁共振(NMR)光谱研究了塑性晶体混合金刚烷衍生物,即氰基金刚烷(75%)和氯金刚烷(25%)的动态性质,温度范围为110 - 420 K,光谱范围覆盖12个数量级。研究了相变,并确定了塑性(I)、玻璃态(Ig)和有序(III)相的动力学参数,并与纯化合物的参数进行了比较。过冷塑性相的动力学特征是α过程呈现阿仑尼乌斯行为,这将混合化合物归类为强玻璃形成剂。在塑性相中,通过使用考虑结构平衡位置的弗伦克尔模型来解释NMR弛豫时间。该模型通过考虑两种分子运动充分解释了实验结果。在玻璃态和塑性相中,运动参数与1-氰基金刚烷的参数一致。相反,在有序相中,与氯金刚烷分子单轴旋转相关的运动参数表明运动加速。