Molecular reorientation of CD 4 in gas‐phase mixtures

Spin‐lattice relaxation times were measured for the deuterons in CD 4 in pure gas and in mixtures with the following buffer gases: Ar, Kr, Xe, HCl, N 2 , CO, CO 2 , CF 4 , and SF 6 . Effective collision cross sections σ θ, 2 for the molecular reorientation of CD 4 in collisions with these ten molecules are obtained as a function of temperature. These cross sections are compared with the corresponding cross sections σ J obtained from 1 H spin‐rotation relaxation in mixtures of CH 4 with the same set of buffer gases. Various classical reorientation models typically applied in liquids predict different ratios of the reduced correlation times for the reorientation of spherical tops. The Langevin model comes closest to predicting the magnitude of the σ θ, 2 /σ J ratio that we obtain for CD 4 . Copyright © 2006 John Wiley & Sons, Ltd.