Spin relaxation of muonium-substituted ethyl radicals (MuCH2ÄŠH2) in the gas phase

Fleming, Donald G.; Pan, James J.; Senba, Masayoshi; Arseneau, Donald J.; Kiefl, Robert F.; Shelley, Mee Y.; Cox, Stephen F. J.; Percival, Paul W.; Brodovitch, Jean-Claude
November 1996
Journal of Chemical Physics;11/1/1996, Vol. 105 Issue 17, p7517
Academic Journal
The spin relaxation of the muonium-substituted ethyl radical (MuCH2ĊH2) and its deuterated analog (MuCD2ĊD2) has been studied in the gas phase in both transverse and longitudinal magnetic fields spanning the range ∼0.5–35 kG, over a pressure range from ∼1–16 atm at ambient temperature. The Mu13CH213ĊH2 radical has also been investigated, at 2.7 atm. For comparison, some data is also reported for the MuCH2Ċ(CH3)2 (Mu-t-butyl) radical at a pressure of 2.6 atm. This experiment establishes the importance of the μSR technique in studying spin relaxation phenomena of polyatomic radicals in the gas phase, where equivalent ESR data is sparse or nonexistent. Both T1 (longitudinal) and T2 (transverse) μSR relaxation rates are reported and interpreted with a phenomenological model. Relaxation results from fluctuating terms in the spin Hamiltonian, inducing transitions between the eigenstates assumed from an isotropic hyperfine interaction. Low-field relaxation is primarily due to the electron, via both the nuclear hyperfine (S·A·I) and the spin rotation interactions (S·J), communicated to the muon via the isotropic muon–electron hyperfine interaction. At the highest fields, direct spin flips of the muon become important, due to fluctuations in the anisotropic part of the muon–electron hyperfine interaction. In the intermediate field region a muon–electron ‘‘flip–flop’’ relaxation mechanism dominates, due partly to the anisotropic hyperfine interaction and partly to modulation of the isotropic muon–electron hyperfine coupling. In the case of the T2 rates, electron relaxation mechanisms dominate over a much wider field range than for the T1 rates, and inhomogeneous line broadening also contributes. The fluctuations that induce both the T1 and T2 relaxation rates are described by a single correlation time, τc, inversely...


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