Translational and rotational diffusion in supercooled orthoterphenyl close to the glass transition

Abstract

Self diffusion coefficients in supercooled orthoterphenyl (OTP) have been determined down toD t =3·10−14 m2s−1 using a1H-NMR technique applying static field gradients up to 53T m−1 In a range of more than two decades theD t values agree with those of photochromic tracer molecules of the same size determined by forced Rayleigh scattering down to the glass transition temperatureT g . A change of mechanism is found for translational diffusion atT c ≈1.2T g whereD t is proportional to the inverse shear viscosityη −1 atT>T c butD t ∼η ξ with ξ=0.75 atT<T c . Rotational correlation times determined by2H-NMR stimulated echo techniques in deuterated OTP remain proportinal toη −1 down toT g . Our results are discussed in relation with mode coupling theory and with models of cooperative motion at the glass transition.