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

• Published in: The Journal of chemical physics 1992-11, Vol.97 (10), p.7730-7742
• Main Authors: BEE, M, RENAULT, A, LAJZEROWICZ-BONNETEAU, J, LE BARS-COMBE, M
• Format: Article
• Language: English
• Subjects: Condensed matter: structure, mechanical and thermal properties; Exact sciences and technology; Low-dimensional structures (superlattices, quantum well structures, multilayers): structure, and nonelectronic properties; Physics; Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties)
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.463492

The nitroxide C9H16NO2 forms channel inclusion compounds with linear hydrocarbons. In particular, alkane molecules CnH2n+2 (if n≥6) can be enclosed end to end in parallel channels (c.a. 5 Å 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 if n≤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 CH2 around 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.