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Dynamics of an inclusion compound of alkyl chains in an organic matrix

机译:有机基质中烷基链夹杂物的动力学

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The nitroxide C9H16NO2forms channel inclusion compounds with linear hydrocarbons. In particular, alkane molecules CnH2n+2(ifn≥6) can be enclosed end to end in parallel channels (c.a. 5 A˚ diameter). At room temperature, disorder of the chains is revealed by diffuse planes on x‐ray photographs. Lock‐in transitions occur at low temperature: one ifn≤14 and two for greater length. Inclusion compounds with shorter chains, heptane and octane, were extensively analyzed. Besides other techniques, neutron experiments were carried out with selectively deuterated samples, in order to access the individual dynamics of the alkane or of the matrix. Advantage was taken of the characteristics of different spectrometers: IN6 and IN5 at Institut Laue‐Langevin in Grenoble, MIBEMOL in Saclay, and IRIS at the Rutherford Appleton Laboratory. We propose a general model for the dynamics of this system. The motion of the alkyl chains combines kink defects responsible for jumps of the CH2around the channel axis, together with a local fast motion of the H atoms, originating from the torsions of the chains and with a component parallel to the channel axis. Moreover, the reorientations of the alkyl chains are clearly related to an inversion of the cycles of the matrix molecules around the channels. Their displacements are evident.
机译:氮氧化物 C9H16NO2 与线性烃形成通道夹杂物。特别是,烷烃分子CnH2n+2(ifn≥6)可以首尾相连地封闭在平行通道中(约5 A&环;直径)。在室温下,链的无序性通过X&连字符射线照片上的漫反射面显示。锁定&连字符;在低温下发生跃迁:一个 ifn≤14 和两个更长的 ifn。对具有较短链的庚烷和辛烷的夹杂物进行了广泛的分析。除其他技术外,还使用选择性氘化样品进行中子实验,以获得烷烃或基质的单个动力学。利用了不同光谱仪的特性:格勒诺布尔的 Institut Laue‐Langevin 的 IN6 和 IN5、萨克雷的 MIBEMOL 和卢瑟福阿普尔顿实验室的 IRIS。我们提出了该系统动力学的一般模型。烷基链的运动结合了导致 CH2 绕通道轴跳跃的扭结缺陷,以及源自链扭转的 H 原子的局部快速运动,并且具有平行于通道轴的分量。此外,烷基链的重新取向显然与通道周围基质分子循环的反转有关。他们的流离失所是显而易见的。

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