Masayoshi Senba

Experimental tests of reaction rate theory: Mu+H2 and Mu+D2

Bimolecular rate constants for the thermal chemical reactions of muonium (Mu) with hydrogen and deuterium—Mu+H2→MuH+H and Mu+D2→MuD+D—over the temperature range 473–843 K are reported. The Arrhenius parameters and 1σ uncertainties for the H2 reaction are log A (cm3 molecule−1 s−1)=−9.605±0.074 and Ea =13.29±0.22 kcal mol−1, while for D2 the values are −9.67±0.12 and 14.73±0.40, respectively. These results are significantly more precise than those reported earlier by Garner et al. For the Mu reaction with H2 our results are in excellent agreement with the 3D quantum mechanical calculations of Schatz on the Liu–Siegbahn–Truhlar–Horowitz potential surface, but the data for both reactions compare less favorably with variational transition‐state theory, particularly at the lower temperatures.

Hyperfine constants for the ethyl radical in the gas phase

Abstract Muon spin rotation and level-crossing spectroscopy have been used to measure the muon, proton, deuteron and 13C hyperfine coupling constants for the isotopically substituted ethyl radicals CH2CH2Mu, CD2CD2Mu and 13CH213CH2Mu in the gas phase.

Reaction kinetics of muonium with the halogen gases (F2, Cl2, and Br2)

Bimolecular rate constants for the thermal chemical reactions of muonium (Mu) with the halogen gases—Mu+X2→MuX+X—are reported over the temperature ranges from 500 down to 100, 160, and 200 K for X2=F2,Cl2, and Br2, respectively. The Arrhenius plots for both the chlorine and fluorine reactions show positive activation energies Ea over the whole temperature ranges studied, but which decrease to near zero at low temperature, indicative of the dominant role played by quantum tunneling of the ultralight muonium atom. In the case of Mu+F2, the bimolecular rate constant k(T) is essentially independent of temperature below 150 K, likely the first observation of Wigner threshold tunneling in gas phase (H atom) kinetics. A similar trend is seen in the Mu+Cl2 reaction. The Br2 data exhibit an apparent negative activation energy [Ea=(−0.095±0.020) kcal mol−1], constant over the temperature range of ∼200–400 K, but which decreases at higher temperatures, indicative of a highly attractive potential energy surface. This...

Muonium addition reactions in the gas phase: Quantum tunneling in Mu + C2H4 and Mu + C2D4

The reaction kinetics for the addition of the muonium (Mu=μ+e−) atom to C2H4 and C2D4 have been measured over the temperature range 150–500 K at (N2) moderator pressures near 1 atm. A factor of about 8 variation in moderator pressure was carried out for C2H4, with no significant change seen in the apparent rate constant kapp, which is therefore taken to be at the high pressure limit, yielding the bimolecular rate constant kMu for the addition step. This is also expected from the nature of the μSR technique employed, which, in favorable cases, gives kapp=kMu at any pressure. Comparisons with the H atom data of Lightfoot and Pilling, and Sugawara et al. and the D atom data of Sugawara et al. reveal large isotope effects. Only at the highest temperatures, near 500 K, is kMu/kH given by its classical value of 2.9, from the mean velocity dependence of the collision rate but at the lowest temperatures kMu/kH≳30/1 is seen, reflecting the pronounced tunneling of the much lighter Mu atom (mμ=1/9 mp). The present M...

A spin rotator for surface μ+ beams on the new M20 muon channel at TRIUMF☆

Abstract The TRIUMF low energy muon channel, M20, was completely rebuilt in 1983. Amongst the features incorporated into the new channel is a 3 m long Wien filter or dc separator. For surface and sub-surface μ + beams, the magnetic field of this device is sufficient to rotate the muon spin from its natural orientation, antiparallel to the beam momentum, by 90° into a transverse orientation. The performance of this muon “spin rotator” is described.

The thermal reaction rate of muonium with methane (and ethane) in the gas phase

Rates for the gas‐phase thermal reaction Mu+CH4→MuH+CH3 (Mu=μ+e−), have been measured using the μSR (muon spin rotation) technique, over the temperature range 625–820 K. A good fit is obtained to the usual Arrhenius expression, k=A exp(−Ea/RT), giving an activation energy Ea=24.6±0.9 kcal/mol, ∼12 kcal/mol higher than that of the H‐atom isotopic variant of this reaction, H+CH4→H2+CH3. This Ea difference is the largest yet seen at high temperatures between H and Mu in the gas phase, and seems much too high to be explained in terms of [zero‐point‐energy (ZPE)] differences in their respective transition states, indicating instead a dramatic difference in reaction dynamics. The possible sources of this difference include differing reactivities from vibrationally excited states and/or a more favorable tunneling path for the H+CH4 reaction due to its suspected much earlier (and thinner) reaction barrier. In contrast, the similar H‐atom abstraction reactions with H2 and C2H6 gave Ea differences which matched exp...

Muon—nuclear quadrupolar level crossing resonance in solid nitrogen. Evidence for N2μ+ ion formation

Abstract Both integral and time-differential muon level crossing resonance techniques were used to identify the source of the diamagnetic μ + SR signal in crystalline nitrogen. When the muon Zeeman splitting and the 14 N nuclear quadrupole splitting are equal, the longitudinal field μ + spin relaxation rate is increased due to dipolar 14 N—μ + coupling. At T = 37 K the resonance occurs at a magnetic field of 172 ± 2 G with a fwhm of 10 ± 2 G. The resonance parameters unambiguously confirm the formation of the N 2 μ + ion in solid nitrogen.

Hyperfine coupling constants of muonium-substituted cyclohexadienyl radicals in the gas phase: C6H6Mu, C6D6Mu, C6F6Mu

Muon spin rotation (μSR) and avoided level crossing resonance (ALCR) have been used to determine the hyperfine coupling constants (hfcs) of the muonium-substituted cyclohexadienyl radicals C6H6Mu, C6D6Mu and C6F6Mu in the gas phase, at pressures ∼1 and 15 atm and temperatures in the range 40–80°C. Equivalent studies of polyatomic free radicals in gases, by electron spin resonance (ESR) spectroscopy, are generally not possible in this pressure range. The present gas phase results support the findings of earlier studies of cyclohexadienyl radicals in the condensed phase, by both μSR and ESR. Minor but not insignificant (∼1%) effects on the hfcs are observed, which can be qualitatively understood for such nonpolar media in terms of their differing polarizabilities. This is the first time that comparisons of this nature have been possible between different phases at the same temperatures. These μSR/ALCR gas-phase results provide a valuable benchmark for computational studies on radicals, free from possible effects of solvent or matrix environments.

Spin relaxation of muonium‐substituted ethyl radicals (MuCH2ĊH2) in the gas phase

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 h...

Spin dynamics of the positive muon radicals in the presence of rapid electron spin exchange: frequency shift and relaxation

The spin dynamics of the positive muon in a muonium-like radical has been investigated in the case where the unpaired electron of the radical undergoes rapid spin flip collisions. If the spin flip rate lambda SF is much faster than the hyperfine frequency of the radical, the behaviour of the muon spin is very similar to that of a positive muon in diamagnetic environments. The field dependence of the relaxation and frequency shift will provide a tool to distinguish experimentally the muon in a radical which behaves like a free positive muon from a genuine diamagnetic muon. The work can be applied to a variety of fields involving muonium and hydrogen, such as spin dynamic in the gas phase and the muonium-like (hydrogen-like) states in semiconductors. The case where the muon undergoes both spin flip and charge transfer collisions is also discussed.