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Updated: Sep 3, 2026

Direct Imaging of Laser-driven Ultrafast Molecular Rotation
Published on: February 4, 2017
REDOR dephasing by multiple spins in the presence of molecular motion
1Department of Chemistry, Washington University, St. Louis, Missouri 63130, USA.
Abstract:
Closed-form, numerical algorithms are presented for calculating REDOR dephasing for three general cases: (i) collections of isolated I-S spin pairs; (ii) many S spins coupled to an I spin; and (iii) an I-S spin pair in relative motion. For the case when more than one S spin is dipolar coupled to an I spin, the calculation assumes that the S-S homonuclear interaction does not affect REDOR dephasing. Full numerical simulations show that this assumption is true if the S-spin lineshapes are inhomogeneously broadened, the S-spin chemical shifts are far from rotational resonance, and a version of REDOR is used which minimizes the number of S-spin pi pulses. For the rapidly rotating -CF3 group of poly(trifluoroethyl methacrylate), the formalisms of (ii) and (iii) are combined to calculate the dephasing. The experimentally measured dephasing matches theory when the wiggling motion of the -OCH2CF3 moiety of the polymer is taken into account.
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