Abstract
High-resolution quasi-elastic neutron-scattering measurements have been made on two nematogens: DMBCA with a nematic range 108 to 119°C, and 5CB and a tail-deuteriated sample (D5CB), having a nematic range 22·6 to 35·1°C.
Results on 5CB in the crystal phase at ∼18°C showed no significant quasielastic broadening, which means that any random motions of the alkyl chain are slower than about 5 × 109 rad s-1. Measurements were made at a single temperature in the nematic phases on specimens aligned in a magnetic field of 0·25T; for DMBCA with scattering vector Q⊥n (n is the nematic director) and for 5CB and D5CB with Q⊥n and Q∥n and also on the isotropic liquid phase of D5CB at 45°C. Analysis of the coherent scattering from nematic D5CB at Q = 1·2 Å-1 and 25°C gave an order parameter <P 2>=0·55, close to the simple mean field value for this temperature. The coherent scattering from DMBCA is too weak to allow this experiment to be performed.
The most remarkable qualitative feature of the results is the close similarity of the scattering law S(Q, ω) for D5CB (and 5CB) with Q⊥n and Q∥n. Analysis of the results in all cases was made using values for the translational diffusion constants measured previously. Corrections for multiple scattering are shown to be important and a single simple model has been devised which fits the line shapes of all the results for D5CB in nematic (Q⊥n and Q∥n) and isotropic liquid phases and DMBCA. The model involves uniaxial rotational diffusion about the long molecular axis m coupled to a displacement along the rotation axis giving a net rotation in a plane whose normal makes an angle ∝ relative to the direction m. Values for the rotational diffusion constant D rd ns-1 are as follows: D5CB, 25°C, 6 (∝ ∼ 50°); 45°C, 10. DMBCA, 112°C, 16, (all ±10–15 per cent).
The results for D5CB and 5CB are so similar that no additional detailed model fitting was attempted for the fully hydrogenous sample and it is concluded that while the motion of the alkyl tails is freer, the time scale of the motions is not more than about a factor of 2 faster than that of the molecular cores.