Synthesis of Bimetallic Copper‐Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit

The structurally precise Cu‐rich hydride nanoclusters [PdCu₁₄H₂(dtc/dtp)₆(C≡CPh)₆] (dtc: di‐butyldithiocarbamate ( 1 ); dtp: di‐isopropyl dithiophosphate ( 2 )) were synthesized from the reaction of polyhydrido copper clusters [Cu₂₈H₁₅(S₂CNⁿBu₂)₁₂]⁺ or [Cu₂₀H₁₁{S₂P(OⁱPr)₂}₉] with phenyl acetylene in the presence of Pd(PPh₃)₂Cl₂. Their structures and compositions were determined by single‐crystal X‐ray diffraction and the results supported by ESI‐mass spectrometry. Hydride positions in 1 were confirmed by single‐crystal neutron diffraction. Each hydride is connected to one Pd⁰ and four Cu^I atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH₂]^2? unit and its Cu₁₄ bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.     

Rapid collapse of spin waves in nonuniform phases of the second Landau level

The spin degree of freedom in quantum phases of the second Landau level is probed by resonant light scattering. The long wavelength spin wave, which monitors the degree of spin polarization, is at the Zeeman energy in the fully spin-polarized state at ν = 3. At lower filling factors, the intensity of the Zeeman mode collapses, indicating loss of polarization. A novel continuum of low-lying excitations emerges that dominates near ν = 8/3 and ν = 5/2. Resonant Rayleigh scattering reveals that quantum fluids for ν < 3 break up into robust domain structures. While the state at ν = 5/2 is considered to be fully polarized, these results reveal unprecedented roles for spin degrees of freedom.     

Modified locus equations categorize stop place in a perceptually realistic time frame

Slope and y-intercepts of locus equations have previously been shown to successfully classify place of articulation for English voiced stop consonants when derived from measurements at vowel onset and vowel midpoint. However, listeners are capable of identifying English voiced stops when less than 30 ms of vowel is presented. The present results show that modified locus equation measurements made within the first several pitch periods of a vowel following an English voiced stop were also successful at classifying place of articulation, consistent with the amount of vocalic information necessary for perceptual identification of English voiced stops /b d g/.     

Hydride-containing 2-Electron Pd/Cu Superatoms as Catalysts for Efficient Electrochemical Hydrogen Evolution

The first hydride-containing 2-electron palladium/copper alloys, [PdHCu₁₁{S₂P(OⁱPr)₂}₆(C≡CPh)₄] ( PdHCu₁₁ ) and [PdHCu₁₂{S₂P(OⁱPr)₂}₅{S₂PO(OⁱPr)} (C≡CPh)₄] ( PdHCu₁₂ ), are synthesized from the reaction of [PdH₂Cu₁₄{S₂P(OⁱPr)₂}₆(C≡CPh)₆] ( PdH₂Cu₁₄ ) with trifluoroacetic acid (TFA). X-ray diffraction reveals that the PdHCu₁₁ and PdHCu₁₂ kernels consist of a central PdH unit encapsulated within a vertex-missing Cu₁₁ cuboctahedron and complete Cu₁₂ cuboctahedron, respectively. DFT calculations indicate that both PdHCu₁₁ and PdHCu₁₂ can be considered as axially-distorted 2-electron superatoms. PdHCu₁₁ shows excellent HER activity, unprecedented within metal nanoclusters, with an onset potential of −0.05 V (at 10 mA cm⁻²), a Tafel slope of 40 mV dec⁻¹, and consistent HER activity during 1000 cycles in 0.5 M H₂SO₄. Our study suggests that the accessible central Pd site is the key to HER activity and may provide guidelines for correlating catalyst structures and HER activity.     

Higher-energy composite fermion levels in the fractional quantum Hall effect

Even though composite fermions in the fractional quantum Hall liquid are well established, it is not yet known up to what energies they remain intact. We probe the high-energy spectrum of the 1/3 liquid directly by resonant inelastic light scattering, and report the observation of a large number of new collective modes. Supported by our theoretical calculations, we associate these with transitions across two or more composite fermions levels. The formation of quasiparticle levels up to high energies is direct evidence for the robustness of topological order in the fractional quantum Hall effect.     

Observation of nonconventional spin waves in composite-fermion ferromagnets

We find unexpected low energy excitations of fully spin-polarized composite-fermion ferromagnets in the fractional quantum Hall liquid, resulting from a complex interplay between a topological order manifesting through new energy levels and a magnetic order due to spin polarization. The lowest energy modes, which involve spin reversal, are remarkable in displaying unconventional negative dispersion at small momenta followed by a deep roton minimum at larger momenta. This behavior results from a nontrivial mixing of spin-wave and spin-flip modes creating a spin-flip excitonic state of composite-fermion particle-hole pairs. The striking properties of spin-flip excitons imply highly tunable mode couplings that enable fine control of topological states of itinerant two-dimensional ferromagnets.     

The photocurrent response of human cones is fast and monophasic

Background  

The precise form of the light response of human cone photoreceptors in vivo has not been established with certainty. To investigate the response shape we compare the predictions of a recent model of transduction in primate cone photoreceptors with measurements extracted from human cones using the paired-flash electroretinogram method. As a check, we also compare the predictions with previous single-cell measurements of ground squirrel cone responses.     

Synthesis of Two‐Electron Bimetallic Cu–Ag and Cu–Au Clusters by using [Cu13(S2CNnBu2)6(C≡CPh)4]+ as a Template

Atomically precise Cu‐rich bimetallic superatom clusters have been synthesized by adopting a galvanic exchange strategy. [Cu@Cu₁₂(S₂CNⁿBu₂)₆(C≡CPh)₄][CuCl₂] ( 1 ) was used as a template to generate compositionally uniform clusters [M@Cu₁₂(S₂CNⁿBu₂)₆ (C≡CPh)₄][CuCl₂], where M=Ag ( 2 ), Au ( 3 ). Structures of 1 , 2 and 3 were determined by single crystal X‐ray diffraction and the results were supported by ESI‐MS. The anatomies of clusters 1 – 3 are very similar, with a centred cuboctahedral cationic core that is surrounded by six di‐butyldithiocarbamate (dtc) and four phenylacetylide ligands. The doped Ag and Au atoms were found to preferentially occupy the centre of the 13‐atom cuboctahedral core. Experimental and theoretical analyses of the synthesized clusters revealed that both Ag and Au doping result in significant changes in cluster stability, optical characteristics and enhancement in luminescence properties.