Recent advances in positive muon spin rotation; muonium as a probe of fullerenes

In non-metallic solids the positive muon often forms paramagnetic muonium centers which are characterized by the hyperfine interactions of the unpaired electron with the positive muon and with the surrounding nuclear spins. The static and fluctuating components of these hyperfine interactions provide information on local molecular dynamics and local electronic structure. Some recent results on C₆₀ and related compounds are presented to illustrate this.     

Level crossing resonance in muonium-like systems

This paper describes the phenomenon of level crossing resonance (or avoided level crossing) encountered in paramagnetic systems involving a muon. Recent experiments on muonated radicals and muonium defect centers in semiconductors are reviewed which demonstrate how the technique provides detailed information on nuclear hyperfine structure, which is unresolvable with more standard techniques. The science implications are discussed.     

Spin relaxation studies of the muonium substituted ethyl radical in the gas phase

This short communication draws attention to the power of μSR and related measurements in providing an unusually complete characterisation of muonium substituted organic radicals in the gas phase. Spectroscopic information is available from muon spin rotation and muon level crossing resonance, giving all the nuclear hyperfine coupling constants, just as in the liquid phase. In addition, measurements of the relaxation time of the muon Zeeman energy become possible; these are potentially informative on the molecular collision dynamics. Demonstration results are presented in summary for the muonium substituted ethyl radical, ĊH₂CH₂Mu, in ethene gas.     

Zero field isotropic Muonium Kubo — Toyabe relaxation functions

Static zero field Gaussian Kubo — Toyabe relaxation functions for muons in isotropic muonium atoms are presented. That is, as with diamagnetic muons, an average of the spin dynamics of a muon in an isolated isotropic ground state muonium atom is taken over an isotropic Gaussian continuous classical local random magnetic field distribution. This motion approximates the exact quantal spin dynamics generated by the dipole-dipole interactions between the muonium atom and the surrounding nuclear spins associated with the site at which the muonium atom has stopped. Expressions are derived for triplet muonium only since, in general, singlet muonium is not observed. For normal nuclear spins and ground state muonium, the resulting relaxation functions are identical to the standard diamagnetic function (except for a shift in the time scale).     

Field dependence of the longitudinal muon polarization for anomalous muonium

The constant muon polarization for anomalous muonium exhibits a peculiar field dependence which represents an easily measurable signature of anomalous muonium centers even in polycrystalline materials. Furthermore it can be used to extract information on the dynamical destruction of the state upon temperature variations and it might also be useful to investigate muonium in amorphous materials.This work has been partially supported by the Swiss National Science Foundation.     

Current trends in muonium chemistry

As “rapporteur” for the papers submitted to this conference in the general area of muonium chemistry, I briefly review the major developments since μSR86, and attempt to show how the papers presented at μSR90 relate to each other and work published in the intervening years. Some topics are discussed in more detail than others, reflecting my own interests and views on what is of current importance. Nevertheless, I try to cover all current research in muonium chemistry. The major areas are: early events following muon thermalization, including subsequent loss of muon polarization (the “missing fraction”); molecular structure and dynamics, primarily of muonium-substituted free radicals: and reaction kinetics.     

Radiofrequency muon depolarization in the muonium + nuclear spin system

The effect of a considerable strengthening of muon depolarization in ALC resonance experiments was predicted for the muonium + nuclear spin system in the presence of a radiofrequency field. A mathematical approach was developed for obtaining analytic solutions that described the muon spin dynamics in ALC experiments, including a particular exact solution that contained much information about the system studied in fairly low magnetic radiofrequency fields. An analysis of these solutions and numerical calculations allowed us to comprehensively analyze muon depolarization patterns in a radiofrequency field. The results reveal the potential of muon depolarization strengthening for considerably increasing the sensitivity of experimental studies of muonium interactions with neighboring nuclear spins and for obtaining new spectroscopic information.     

Muonium acoustic resonance

Theoretical consideration is given to the effect of ultrasonic oscillations on the spin polarization of the positive muon of muonium present in matter. The resonant action of the periodic acoustic perturbation on the muonium hyperfine structure levels is shown to result in characteristic oscillations and to modify the muon spin precession pattern considerably. The possibilities for experimental detection of the muonium acoustic resonance are discussed     

Charge exchange of muons in gases: Experimental implications from rate theory

The effects of the charge exchange process on muon spin dynamics have been investigated using a density operator formalism with special interest placed upon the diamagnetic muon and paramagnetic muonium signals observed after thermalization. In the charge exchange region the dynamics of the spin density operator is assumed to be determined by the muonium hyperfine interaction and by electron capture and loss processes for muons. Analytical expressions are obtained for the amplitudes and phases of the diamagnetic muon and paramagnetic muonium signals as a function of the duration of the charge exchange region,t _c, which is inversely proportional to the number density of the moderating gas. The theoretical signals exhibit three features which have, as yet, to be experimentally observed, namely: (i) that the amplitudes associated with the muonium Larmor frequency and with the hyperfine frequency are not, in general, equal, (ii) that all the amplitudes are, in general, damped oscillatory functions oft _c (temperature/pressure) and (iii) that phase jumps occur when an amplitude decreases to zero and then increases with falling pressure. Fits to the experimental argon data are discussed in light of the above points.     

Atomic hydrogen and muonium in alkali halides

Atomic hydrogen can be trapped at interstitial and substitutional cation and anion sites in alkali halides. The geometrical structure of these defects was established by electron nuclear double resonance (ENDOR). From the analysis of the ENDOR spectra also detailed information was obtained on the electronic structure. In this article the major experimental and theoretical results for atomic hydrogen in several alkali halides are briefly reviewed. Special emphasis is given to the isotope effects upon replacing hydrogen by deuterium. The nature of the dynamical hyperfine and superhyperfine interactions is discussed. Its magnitude to be expected for muonium is estimated. Recent results on muonium centres are discussed on the basis of the knowledge about the hydrogen centres.     

Influence of impurities on short range electron transport in GaAs

The influence of Cr impurities on muonium atom formation in GaAs has been studied using muon spin relaxation techniques with alternating electric fields. The results suggest that electron transport to and capture by the muon is suppressed by capture/scattering on intervening Cr centers. The length scale involved is estimated to be about 3x10(-6) cm. This offers an opportunity to study electron transport to positive centers in semiconductors on a microscopic scale.     

Hydrogen and muonium in silicon

First principles calculations of the properties of hydrogen and muonium in silicon are presented. H⁺ and H⁻ are shown to have definite preferences for bond-centred and tetrahedral interstitial sites respectively whereas H⁰ (or a muon) is shown to be stable at two sites with almost equal energies, the bond-centred and antibonding sites. The structures of normal and isotropic muonium are discussed. In contrast to common belief the tetrahedral site is shown to be unstable with the muon moving spontaneously towards one of the neighbouring silicon atoms. The barrier to motion between equivalent antibonding sites is low suggesting that the normal muonium signal is isotropic because of motional averaging, not due to the symmetry of a well defined equilibrium site.     

Electronic structure and dynamics of muonium in semiconductors

In this paper, a selection of recent results on muonium in semiconductors is presented. These are primarily taken from Si and GaAs and encompass the electronic structure of the diamagnetic centers, charge state cycling, spin‐exchange scattering and interconversion between muonium states. These experiments illustrate the power of μSR for investigating the behavior of muonium and, by analogy, the technologically relevant isolated hydrogen centers in semiconductors. This revised version was published online in August 2006 with corrections to the Cover Date.     

Calculations of the hyperfine parameters of bond-centered muonium in diamond

The electronic structure of hydrogen and muonium at the bond-centered site in diamond is investigated using ab initio cluster calculations. Correlation effects are accounted for by a configuration interaction expansion and by the local density approximation in the density functional approach. The hyperfine and superhyperfine parameters for anomalous muonium are determined by averaging over the spread of the muon wave function. Good agreement with experimental hyperfine parameters is found.This work has partially been supported by the Swiss National Science Foundation.     

Local structure of isolated positively charged muonium as an analog for the hydrogen ion in p-type GaAs

We determine the local structure of isolated positively charged muonium (Mu+) in heavily doped p-type GaAs based on muon level crossing resonance and zero applied field muon spin depolarization data. These measurements provide the first direct experimental confirmation that Mu+, and by analogy H+, is located within a stretched Ga-As bond. The distances between Mu+ and the nearest neighbor Ga and As atoms are estimated to be 1.83 +/- 0.10 A; and 1.76 +/- 0.10 A, respectively. These results are compared to existing theoretical calculations on the structure of hydrogen in GaAs and additionally provide data on the induced electric field gradients.     

Fullerenes with μSR

The current status ofSR results on muonium states in the pure fullerenes C₆₀ and C₇₀ is summarized. The hyperfine interaction between the unpaired electron and the muon provides unique information on the molecular dynamics and local electronic structure of the fullerenes. Recent results on the alkali doped C₆₀ series are also presented.     

Muonium in semiconductors: Recent experimental developments

Recent experiments covering a range of problems including the nuclear hyperfine structure of bond-centered muonium in diamond and GaP, charge-cycling reactions of muonium in Si at high temperatures, muonium state dynamics in Si probed by RF-SR, and endohedral muonium in semiconducting C₆₀ compounds, are discussed. These examples show that as traditionalSR techniques are continually being refined and new methods are being developed,SR is becoming an increasingly powerful tool to investigate the behavior of muonium and the in many respects analogous, and technologically relevant, hydrogen centers in semiconductors.     

Theory for position of muonium in α-quartz and associated hyperfine interaction

The electronic structures and hyperfine interactions of muonium and hydrogen in -quartz are investigated by the unrestricted Hartree-Fock cluster procedure. The muonium is found to be trapped near the center of the line joining two silicon atoms. On including vibrational effects, the muon hyperfine constant comes out as 1.09 times that for free muonium, this ratio being larger than unity and smaller than for protons in trapped hydrogen, both features being in agreement with experiment.Briefly reported in Abstract at the American Physical Society meeting in New Orleans, March 1988. See Bull. Am. Phys. Soc. 33 (1988) 770.     

Diffusion of muonium and hydrogen in diamond

Jump rates of muonium and hydrogen in diamond are calculated by quantum transition-state theory, based on the path-integral centroid formalism. This technique allows us to study the influence of vibrational mode quantization on the effective free-energy barriers DeltaF for impurity diffusion, which are renormalized with respect to the zero-temperature classical calculation. For the transition from a tetrahedral (T) site to a bond-center (BC) position, DeltaF is larger for hydrogen than for muonium, and the opposite happens for the transition BC-->T. The calculated effective barriers decrease for rising temperature, except for the muonium transition from T to BC sites. The calculated jump rates are in good agreement with available muon spin rotation data.