On the role of collective and local molecular fluctuations in the relaxation of proton intrapair dipolar order in nematic 5CB

O. MENSIO, R. C. ZAMAR, E. ANOARDO, R. H. ACOSTA Y R. Y. DONG

JOURNAL OF CHEMICAL PHYSICS

Año: 2005 vol. 123 p. 1 - 9

0021-9606

We investigate the role that local motions and slow cooperative fluctuations have on the relaxation of the intrapair dipolar order in the nematic 5CB. With this purpose we present a theoretical and experimental systematic study which allow us to quantify the contribution from each type of molecular fluctuation to the intrapair dipolar order relaxation time, T1D. The experimental work includes measurements of Zeeman and intrapair dipolar order relaxation times (T1Z and T1D) as a function of temperature at conventional NMR frequencies, in three complementary samples: normal and chain deuterated 4-n-pentyl-4 -cyanobiphenyl (5CB and 5CBd11) and a mixture of normal 5CB and fully deuterated 4-n-pentyl-4 -cyanobiphenyl (5CBd19), 50% in weight. Additionally we perform T1Z field-cycling Larmor frequency-dependent measurements to obtain the spectral density of the cooperative fluctuations. The obtained results are as follows. (a) The cooperative molecular fluctuations have a strong relative weight in the relaxation of the intrapair dipolar order state, even at Larmor frequencies in the range of conventional NMR. (b) Alkyl chain rotations are an important relaxation mechanism of the intrapair dipolar order at megahertz frequencies. (c) Intermolecular fluctuations mediated by translational self-diffusion of the molecules is not an efficient mechanism of relaxation of the intrapair dipolar order.