More Like this

1. Spectroscopic and Crystallographic Characterization of the R 3 N + −C−H⋅⋅⋅X Interaction

   https://doi.org/10.1002/chem.202103922  

   Capilato, Joseph N. ; Harry, Stefan A. ; Siegler, Maxime A. ; Lectka, Thomas ( January 2022 , Chemistry – A European Journal)

   As appreciation for nonclassical hydrogen bonds has progressively increased, so have efforts to characterize these interesting interactions. Whereas several kinds of C−H hydrogen bonds have been well‐studied, much less is known about the R₃N⁺−C−H⋅⋅⋅X variety. Herein, we present crystallographic and spectroscopic evidence for the existence of these interactions, with special relevance to Selectfluor chemistry. Of particular note is the propensity for Lewis bases to engage in nonclassical hydrogen bonding over halogen bonding with the electrophilic F atom of Selectfluor. Further, the first examples of¹H NMR experiments detailing R₃N⁺−C−H⋅⋅⋅X (X=O, N) hydrogen bonds are described.

    

   more » « less
2. Plasma-droplet interaction study to assess transport limitations and the role of ⋅ OH, O ⋅ ,H ⋅ ,O 2 (a 1 Δ g ),O 3 , He(2 3 S) and Ar(1s 5 ) in formate decomposition

   https://doi.org/10.1088/1361-6595/ac2676  

   Nayak, Gaurav ; Oinuma, Gaku ; Yue, Yuanfu ; Santos Sousa, João ; Bruggeman, Peter J ( November 2021 , Plasma Sources Science and Technology)

   Abstract Plasmas interacting with liquid microdroplets are gaining momentum due to their ability to significantly enhance the reactivity transfer from the gas phase plasma to the liquid. This is, for example, critically important for efficiently decomposing organic pollutants in water. In this contribution, the role of ⋅ OH as well as non- ⋅ OH-driven chemistry initiated by the activation of small water microdroplets in a controlled environment by diffuse RF glow discharge in He with different gas admixtures (Ar, O 2 and humidified He) at atmospheric pressure is quantified. The effect of short-lived radicals such as O ⋅ and H ⋅ atoms, singlet delta oxygen (O 2 ( a 1 Δ g )), O 3 and metastable atoms of He and Ar, besides ⋅ OH radicals, on the decomposition of formate dissolved in droplets was analyzed using detailed plasma diagnostics, droplet characterization and ex situ chemical analysis of the treated droplets. The formate decomposition increased with increasing droplet residence time in the plasma, with ∼70% decomposition occurring within ∼15 ms of the plasma treatment time. The formate oxidation in the droplets is shown to be limited by the gas phase ⋅ OH flux at lower H 2 O concentrations with a significant enhancement in the formate decomposition at the lowest water concentration, attributed to e − /ion-induced reactions. However, the oxidation is diffusion limited in the liquid phase at higher gaseous ⋅ OH concentrations. The formate decomposition in He/O 2 plasma was similar, although with an order of magnitude higher O ⋅ radical density than the ⋅ OH density in the corresponding He/H 2 O plasma. Using a one-dimensional reaction–diffusion model, we showed that O 2 ( a 1 Δ g ) and O 3 did not play a significant role and the decomposition was due to O ⋅ , and possibly ⋅ OH generated in the vapor containing droplet-plasma boundary layer. 

   more » « less
3. Recycled Components in Mantle Plumes Deduced From Variations in Halogens (Cl, Br, and I), Trace Elements, and 3 He/ 4 He Along the Hawaiian‐Emperor Seamount Chain

   https://doi.org/10.1029/2018GC007959  

   Broadley, Michael W. ; Sumino, Hirochika ; Graham, David W. ; Burgess, Ray ; Ballentine, Chris J. ( January 2019 , Geochemistry, Geophysics, Geosystems)

   Halogens are primarily located within surface reservoirs of the Earth; as such they have proven to be effective tracers for the identification of subducted volatiles within the mantle. Subducting lithologies exhibit a wide variety of halogen compositions, yet the mantle maintains a fairly uniform signature, suggesting halogens may be homogenized during subduction to the mantle or during eruption. Here we present halogen (Cl, Br, and I), K, noble gas, and major and trace element data on olivines from three seamounts along the Hawaiian‐Emperor seamount chain to determine if the deep mantle source has retained evidence of halogen heterogeneities introduced through subduction. High Ni contents indicate that the Hawaiian‐Emperor mantle source contains a recycled oceanic crust component in the form of pyroxenite, which increases from the 46% in the oldest (Detroit) to 70% in the younger seamount (Koko). Detroit seamount retains mid‐ocean ridge basalts (MORB)‐like Br/Cl and I/Cl, while the Br/Cl and I/Cl of Suiko and Koko seamounts are higher than MORB and similar to altered oceanic crust and dehydrated serpentinite. Helium isotopes show a similar evolution, from MORB‐like values at Detroit seamount toward higher values at Suiko and Koko seamounts. The correlation between pyroxenite contributions, Br/Cl, I/Cl, and³He/⁴He indicates that subducted material has been incorporated into the primordial undegassed Hawaiian mantle plume source. The identification of recycled oceanic crustal signatures in both the trace elements and halogens indicates that subduction and dehydration of altered oceanic crust may exert control on the cycling of volatile elements to the deep mantle.

    

   more » « less
4. Weyl Fermions and broken symmetry phases of laterally confined 3 He films

   https://doi.org/10.1088/1361-648X/acf42b  

   Wu, Hao ; Sauls, J. A. ( September 2023 , Journal of Physics: Condensed Matter)

   Broken symmetries in topological condensed matter systems have implications for the spectrum of Fermionic excitations confined on surfaces or topological defects. The Fermionic spectrum of confined (quasi-2D)³He-A consists of branches of chiral edge states. The negative energy states are related to the ground-state angular momentum,$L_z=(N/2)\hslash$, for$N/2$Cooper pairs. The power law suppression of the angular momentum,$L_z(T)\simeq (N/2)\hslash [1-\frac{2}{3}(\pi T/\mathrm{\Delta }{)}^2]$for$0⩽T\ll T_c$, in the fully gapped 2D chiral A-phase reflects the thermal excitation of the chiral edge Fermions. We discuss the effects of wave function overlap, and hybridization between edge states confined near opposing edge boundaries on the edge currents, ground-state angular momentum and ground-state order parameter of superfluid³He thin films. Under strong lateral confinement, the chiral A phase undergoes a sequence of phase transitions, first to a pair density wave (PDW) phase with broken translational symmetry at$D_{c2}\sim 16{\xi }_0$. The PDW phase is described by a periodic array of chiral domains with alternating chirality, separated by domain walls. The period of PDW phase diverges as the confinement length$D\to D_{c_2}$. The PDW phase breaks time-reversal symmetry, translation invariance, but is invariant under the combination of time-reversal and translation by a one-half period of the PDW. The mass current distribution of the PDW phase reflects this combined symmetry, and originates from the spectra of edge Fermions and the chiral branches bound to the domain walls. Under sufficiently strong confinement a second-order transition occurs to the non-chiral ‘polar phase’ at$D_{c1}\sim 9{\xi }_0$, in which a single p-wave orbital state of Cooper pairs is aligned along the channel.

    

   more » « less
5. (U‐Th)/He and 4 He/ 3 He Thermochronology of Secondary Oxides in Faults and Fractures: A Regional Perspective From Southeastern Arizona

   https://doi.org/10.1029/2021GC009905  

   Scoggin, Shane H. ; Reiners, Peter W. ; Shuster, David L. ; Davis, George H. ; Ward, Lauren A. ; Worthington, James R. ; Nickerson, Phillip A. ; Evenson, Nathan S. ( November 2021 , Geochemistry, Geophysics, Geosystems)

   Fe‐ and Mn‐oxides are common secondary minerals in faults, fractures, and veins and potentially record information about the timing of fluid movement through their host rocks. These phases are difficult to date by most radioisotopic techniques, but relatively high concentrations of U and Th make the (U‐Th)/He system a promising approach. We present new petrographic, geochronologic and thermochronologic analyses of secondary oxides and associated minerals from fault zones and fractures in southeastern Arizona. We use these phases in attempt to constrain the timing of fluid flow and their relationship to magmatic, tectonic, or other regional processes. In the shallowly exhumed Galiuro Mountains, Fe‐oxide (U‐Th)/He dates correspond to host‐rock crystallization and magmatic intrusions from ca. 1.6 to 1.1 Ga. Step‐heating⁴He/³He experiments and polydomain diffusion modeling of³He release spectra on these samples are consistent with a crystallite size control on He diffusivity, and little fractional loss of radiogenic He since formation in coarse‐grained hematite, but large losses from fine‐grained Mn‐oxide. In contrast to Proterozoic dates, Fe‐ and Mn‐oxides from the Catalina‐Rincon and Pinaleño metamorphic core complexes are exclusively Cenozoic, with dates clustering at ca. 24, 15, and 9 Ma, which represent distinct cooling or fluid‐flow episodes during punctuated periods of normal faulting. Finally, a subset of Fe‐oxides yield dates of ca. 5 Ma to 6 ka and display either pseudomorphic cubic forms consistent with oxidative retrogression of original pyrite or magnetite, or fine‐grained botryoidal morphologies that we interpret to represent approximate ages of recrystallization or pseudomorphic replacement at shallow depths.

    

   more » « less