Journal of Chemical Physics, Vol.106, No.17, 7352-7361, 1997
A Simplified Approach to the Interpretation of Nuclear-Spin Correlations in Entangled Polymeric Liquids
We derive closed-form expressions for a sine correlation function beta(2 tau,tau) which is particularly sensitive to modulations of nuclear dipolar (and quadrupolar) interactions caused by slow molecular reorientations. This function is placed in the context of traditional nuclear magnetic resonance (NMR) experiments-the Free Induction Decay R(t) and the solid echo amplitude E(tau) and families of expressions are evaluated for (i) motion governed by an exponential correlation function and (ii) macromolecular motion dominated by reptation. We introduce a simple correlation function for reptation that depends on only two parameters, (M-2) over bar, the preaveraged dipolar interaction strength and tau(d), the tube disengagement time. From proton NMR measurements of beta in poly(dimethyl siloxane) melts we estimate (M-2) over bar=1.3x10(6) s(-2) and tau(d)=0.019 s at 300 K, in reasonable agreement with a calculated value for (M-2) over bar and an independent NMR estimate of the terminal relaxation time.