Ji, F.

Muon hyperfine constants A_μ have been measured by transverse field μSR for (CH3)3Si\mbox\.CHMu in hexane from 167 K to 332 K. In addition, avoided level‐crossing resonance was used to determine \alpha‐proton coupling constants Ap over a similar range of temperatures. The two hyperfine constants can be described by a common temperature dependence, d|Ai|/ dT=1.4\times 10-3 MHz\,K-1, where Ai represents Ap or the reduced muon constant A^\prime_μ=0.3141A_μ. There is a small isotope effect (A^\prime_μ is 2.2 % larger than Ap) consistent with zero‐point motion in the anharmonic C–H bond stretch. The common temperature dependence is tentatively attributed to a coupled deviation of the C–H and C–Mu bonds out of the nodal plane of the p orbital containing the unpaired electron.

Muon irradiation of pure liquid 3‐chloropropene, CH2=CH-CH2Cl, yields a primary radical, \dot\mboxCH2-CHMu-CH2Cl, and a secondary radical, MuCH2-\rm\dot\mboxCH-CH2Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH2-\rm\dot\mboxC(CH3)-CH2Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH3,-CH2Cl and -CH2Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H.