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This paper describes muon spin spectroscopy studies of 12-phosphatetraphene stabilized by a peri-trifluoromethyl group and a meso-aryl substituent. Even though the prepared solution in tetrahydrofuran (THF) was quite dilute (0.060 M) for transverse-field muon spin rotation (TF-µSR) measurements, the π-extended heavier congener of tetraphene presented a pair of signals due to a muoniated radical from which the muon hyperfine coupling constant (hfc) was determined. This muoniated radical was produced by the diffusion-controlled regioselective addition of muonium (Mu = [µ + e - ]) to the sp 2 -hybridized phosphorus atom. The assignment of the muoniated radical structure was confirmed by observing a resonance due to the I = 1/2 ( 31 P) nucleus in a muon (avoided) level-crossing resonance (µLCR) spectrum. The 31 P hfc was determined from the resonance position, and a comparison with the value obtained from density functional theory (DFT) calculations indicated that the radical retained a flat π-delocalized tetracyclic skeleton. This higher energy structure is hypothesized to be preferable because of the increased zero-point energy of the light mass of the muon. The findings of this study could be fruitful in developing novel spin-functional materials featuring efficient radical capture and π-delocalized paramagnetic molecular systems., Competing Interests: Declarations. Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

We report direct measurements of the magnetic field screening at the limits of the Meissner phase for two superconducting niobium (Nb) samples. The samples are processed with two different surface treatments that have been developed for superconducting radio-frequency (SRF) cavity applications-a "baseline" treatment and an oxygen-doping ("O-doping") treatment. The measurements show: (1) that the screening length is significantly longer in the "O-doping" sample compared to the "baseline" sample; (2) that the screening length near the limits of the Meissner phase increases with applied field; (3) the evolution of the screening profile as the material transitions from the Meissner phase to the mixed phase; and (4) a demonstration of the absence of any screening profile for the highest applied field, indicative of the full flux entering the sample. Measurements are performed utilizing the β -detected nuclear magnetic resonance ( β -NMR) technique that allows depth resolved studies of the local magnetic field within the first 100 nm of the surface. The study takes advantage of the β -SRF beamline, a new facility at TRIUMF, Canada, where field levels up to 200 mT are available parallel to the sample surface to replicate radio frequency fields near the Meissner breakdown limits of Nb., (© 2024. The Author(s).)

The nanoviscosity experienced by molecules in solution may be determined through measurement of the molecular rotational correlation time, τ c , for example, by fluorescence and NMR spectroscopy. With this work, we apply PAC spectroscopy to determine the rate of rotational diffusion, λ=1/τ c , of a de novo designed protein, TRIL12AL16C, in solutions with viscosities, ξ, from 1.7 to 88 mPa⋅s. TRIL12AL16C was selected as molecular probe because it exhibits minimal effects due to intramolecular dynamics and static line broadening, allowing for exclusive elucidation of molecular rotational diffusion. Diffusion rates determined by PAC data agree well with literature data from fluorescence and NMR spectroscopy, and scales linearly with 1/ξ in agreement with the Stokes-Einstein-Debye model. PAC experiments require only trace amounts (∼10 11 ) of probe nuclei and can be conducted over a broad range of sample temperatures and pressures. Moreover, most materials are relatively transparent to γ-rays. Thus, PAC spectroscopy could find applications under circumstances where conventional techniques cannot be applied, spanning from the physics of liquids to in-vivo biochemistry., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A new high field spectrometer has been built to extend the capabilities of the β-detected nuclear magnetic resonance (β-NMR) facility at TRIUMF. This new beamline extension allows β-NMR spectroscopy to be performed with fields up to 200 mT parallel to a sample's surface (perpendicular to the ion beam), allowing depth-resolved studies of local electromagnetic fields with spin polarized probes at a much higher applied magnetic field than previously available in this configuration. The primary motivation and application is to allow studies of superconducting radio frequency (SRF) materials close to the critical fields of Nb metal, which is extensively used to fabricate SRF cavities. The details of the design considerations and implementation of the ultra-high vacuum (UHV) system, ion optics, and beam diagnostics are presented here. Commissioning of the beamline and spectrometer with radioactive ions are also reported here. Future capabilities and applications in other areas are also described.

The complexation of Mg II with adenosine 5'-triphosphate (ATP) is omnipresent in biochemical energy conversion, but is difficult to interrogate directly. Here we use the spin- 1 / 2 β-emitter 31 Mg to study Mg II -ATP complexation in 1-ethyl-3-methylimidazolium acetate (EMIM-Ac) solutions using β-radiation-detected nuclear magnetic resonance (β-NMR). We demonstrate that (nuclear) spin-polarized 31 Mg, following ion-implantation from an accelerator beamline into EMIM-Ac, binds to ATP within its radioactive lifetime before depolarizing. The evolution of the spectra with solute concentration indicates that the implanted 31 Mg initially bind to the solvent acetate anions, whereafter they undergo dynamic exchange and form either a mono- ( 31 Mg-ATP) or di-nuclear ( 31 MgMg-ATP) complex. The chemical shift of 31 Mg-ATP is observed up-field of 31 MgMg-ATP, in accord with quantum chemical calculations. These observations constitute a crucial advance towards using β-NMR to probe chemistry and biochemistry in solution., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

We investigated the depth, temperature, and molecular-weight (MW) dependence of the γ-relaxation in polystyrene glasses using implanted 8 Li + and β-detected nuclear magnetic resonance. Measurements were performed on thin films with MW ranging from 1.1 to 641 kg/mol. The temperature dependence of the average 8 Li spin-lattice relaxation time (T 1 avg ) was measured near the free surface and in the bulk. Spin-lattice relaxation is caused by phenyl ring flips, which involve transitions between local minima over free-energy barriers with enthalpic and entropic contributions. We used transition state theory to model the temperature dependence of the γ-relaxation, and hence T 1 avg . There is no clear correlation of the average entropy of activation (Δ ‡ S̄) and enthalpy of activation (Δ ‡ H̄) with MW, but there is a clear correlation between Δ ‡ S̄ and Δ ‡ H̄, i.e., entropy-enthalpy compensation. This results in the average Gibbs energy of activation, Δ ‡ Ḡ, being approximately independent of MW. Measurements of the temperature dependence of T 1 avg as a function of depth below the free surface indicate the inherent entropic barrier, i.e., the entropy of activation corresponding to Δ ‡ H̄ = 0, has an exponential dependence on the distance from the free surface before reaching the bulk value. This results in Δ ‡ Ḡ near the free surface being lower than the bulk. Combining these observations results in a model where the average fluctuation rate of the γ-relaxation has a "double-exponential" depth dependence. This model can explain the depth dependence of 1/T 1 avg in polystyrene films. The characteristic length of enhanced dynamics is ∼6 nm and approximately independent of MW near room temperature.

We have studied a mosaic of 1T-CrSe 2 single crystals using β-detected nuclear magnetic resonance of 8 Li from 4 to 300 K. We identify two broad resonances that show no evidence of quadrupolar splitting, indicating two magnetically distinct environments for the implanted ion. We observe stretched exponential spin lattice relaxation and a corresponding rate (1/ T 1 ) that increases monotonically above 200 K, consistent with the onset of ionic diffusion. A pronounced maximum in 1/ T 1 is observed at the low temperature magnetic transition near 20 K. Between these limits, 1/ T 1 exhibits a broad minimum with an anomalous absence of strong features in the vicinity of structural and magnetic transitions between 150 and 200 K. Together, the results suggest 8 Li + site occupation within the van der Waals gap between CrSe 2 trilayers. Possible origins of the two environments are discussed., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We report measurements of the diffusion rate of isolated ion-implanted ^{8}Li^{+} within ∼120  nm of the surface of oriented single-crystal rutile TiO_{2} using a radiotracer technique. The α particles from the ^{8}Li decay provide a sensitive monitor of the distance from the surface and how the depth profile of ^{8}Li evolves with time. The main findings are that the implanted Li^{+} diffuses and traps at the (001) surface. The T dependence of the diffusivity is described by a bi-Arrhenius expression with activation energies of 0.3341(21) eV above 200 K, whereas at lower temperatures it has a much smaller barrier of 0.0313(15) eV. We consider possible origins for the surface trapping, as well the nature of the low-T barrier.

NMR spectra of Mg2+ ions in ionic liquids were recorded using a highly sensitive variant of NMR spectroscopy known as β-NMR. The β-NMR spectra of MgCl2 in EMIM-Ac and EMIM-DCA compare favourably with conventional NMR, and exhibit linewidths of ∼3 ppm, allowing for discrimination of species with oxygen and nitrogen coordination.

There is indirect evidence that the dynamics of a polymer near a free surface are enhanced compared with the bulk but there are few studies of how dynamics varies with depth. β-Detected nuclear spin relaxation of implanted 8Li+ has been used to directly probe the temperature and depth dependence of the γ-relaxation mode, which is due to phenyl rings undergoing restricted rotation, in thin films of atactic deuterated polystyrene (PS-d8) and determine how the depth dependence of dynamics is affected by sample processing, such as annealing, floating on water and the inclusion of a surfactant, and by the presence of a buried interface. The activation energy for the γ-relaxation process is lower near the free surface. Annealing the PS-d8 films and then immersing in water to mimic the floating procedure used to transfer films had negligible effects on the thickness of the region near the free surface with enhanced mobility. Measurements on a bilayer film indicate enhanced phenyl ring dynamics near the buried interface compared with a single film at the same depth. PS-d8 films annealed with the surfactant sodium dodecyl sulfate (SDS) deposited on the surface show enhanced dynamics in the bulk compared with a pure PS-d8 film and a PS-d8 film where the SDS was washed away. There is less contrast between the surface and bulk in the SDS-treated sample, which could account for the elimination of the Tg confinement effect observed in films containing SDS [Chen and Torkelson, Polymer, 2016, 87, 226].

By measuring the prototypical antiferromagnet α-Fe_{2}O_{3}, we show that it is possible to determine the static spin orientation and dynamic spin correlations within nanometers from an antiferromagnetic surface using the nuclear spin polarization of implanted ^{8}Li^{+} ions detected with β-NMR. Remarkably, the first-order Morin spin reorientation in single crystal α-Fe_{2}O_{3} occurs at the same temperature at all depths between 1 and 100 nm from the (110) surface; however, the implanted nuclear spin experiences an increased 1/T_{1} relaxation rate at shallow depths revealing soft-surface magnons. The surface-localized dynamics decay towards the bulk with a characteristic length of ε=11±1  nm, closely matching the finite-size thresholds of hematite nanostructures.