QUASI-ELASTIC NEUTRON-SCATTERING MEASUREMENTS OF N-BUTANE IN ITS CRYSTALLINE, PLASTIC, AND LIQUID-PHASES

We report here measurements of quasielastic neutron scattering from n-butane at temperatures of 90, 115, 125 and 190 K and in a momentum transfer range of 0.8-2.4 angstrom-1. These measurements confirm that between 115 and 125 K butane forms a plastic crystal in which the centers of mass of the butane molecules form a crystalline structure, but the individual molecules are free to rotate. At these two intermediate temperatures, there exists both an elastic peak, characteristic of a solid structure, and quasielastic components arising from the rotational motions of the butane molecules. At 90 K, the butane scatters neutrons only elastically, while at 190 K, the butane scatters neutrons only quasielastically. In both the plastic and the liquid phases, the presence of at least two quasielastic processes must be assumed in order to explain the measurements. In the plastic crystal, we associate a broad Lorentzian component with intramolecular reorientations about the central carbon-carbon bond and a second, relatively narrow, Lorentzian component with whole molecule rotations. The latter process gives rise to a rotational quasielastic peak having a width of 400-mu-eV, which is constant to within the instrumental resolution of 70-mu-eV at both temperatures and at all measured momentum transfers. In a continuous diffusion model, this width corresponds to a rotational diffusion constant of 0.277 rad2/ps, a value which is about 3.5 times larger than one extracted from a molecular dynamics simulation of n-butane in the plastic phase recently published by Refson and Pawley [Mol. Phys. 61, 669 (1987); 61, 693 (1987)]. On the other hand, the first process, which corresponds to the carbon-carbon reorientation peak, is about 16 meV wide, indicating that this reorientation occurs on a time scale of about 0.1 ps. The absence of this broad peak in the solid butane at 90 K indicates that this fast carbon-carbon reorientation is coupled to an aspect of the structure or dynamics of the plastic phase. In the scattering from liquid butane at 190 K, there is a third, narrow quasielastic peak which also has a Lorentzian energy distribution. This peak width is about 200-mu-eV and corresponds to a translational diffusion constant of 0.23 angstrom 2/ps, a result in rough agreement with a recent molecular dynamics simulation of liquid butane by Ullo and Yip. [J. Chem. Phys. 85, 4056 (1986)].