A combined "electrochemical-frustrated Lewis pair" approach to hydrogen activation: surface catalytic effects at platinum electrodes

Herein, we extend our “combined electrochemical–frustrated Lewis pair” approach to include Pt electrode surfaces for the first time. We found that the voltammetric response of an electrochemical–frustrated Lewis pair (FLP) system involving the B(C6F5)3/[HB(C6F5)3]− redox couple exhibits a strong surface electrocatalytic effect at Pt electrodes. Using a combination of kinetic competition studies in the presence of a H atom scavenger, 6-bromohexene, and by changing the steric bulk of the Lewis acid borane catalyst from B(C6F5)3 to B(C6Cl5)3, the mechanism of electrochemical–FLP reactions on Pt surfaces was shown to be dominated by hydrogen-atom transfer (HAT) between Pt, [Pt[BOND]H] adatoms and transient [HB(C6F5)3]⋅ electrooxidation intermediates. These findings provide further insight into this new area of combining electrochemical and FLP reactions, and proffers additional avenues for exploration beyond energy generation, such as in electrosynthesis

Near-field photocurrent nanoscopy on bare and encapsulated graphene

Opto-electronic devices utilizing graphene have already demonstrated unique capabilities, which are much more difficult to realize with conventional technologies. However, the requirements in terms of material quality and uniformity are very demanding. A major roadblock towards high-performance devices are the nanoscale variations of graphene properties, which strongly impact the macroscopic device behaviour. Here, we present and apply opto-electronic nanoscopy to measure locally both the optical and electronic properties of graphene devices. This is achieved by combining scanning near-field infrared nanoscopy with electrical device read-out, allowing infrared photocurrent mapping at length scales of tens of nanometers. We apply this technique to study the impact of edges and grain boundaries on spatial carrier density profiles and local thermoelectric properties. Moreover, we show that the technique can also be applied to encapsulated graphene/hexagonal boron nitride (h-BN) devices, where we observe strong charge build-up near the edges, and also address a device solution to this problem. The technique enables nanoscale characterization for a broad range of common graphene devices without the need of special device architectures or invasive graphene treatment

A survey of spectral models of gravity coupled to matter

This is a survey of the historical development of the Spectral Standard Model and beyond, starting with the ground breaking paper of Alain Connes in 1988 where he observed that there is a link between Higgs fields and finite noncommutative spaces. We present the important contributions that helped in the search and identification of the noncommutative space that characterizes the fine structure of space-time. The nature and properties of the noncommutative space are arrived at by independent routes and show the uniqueness of the Spectral Standard Model at low energies and the Pati-Salam unification model at high energies.Comment: An appendix is added to include scalar potential analysis for a Pati-Salam model. 58 Page

Random Exchange Disorder in the Spin-1/2 XXZ Chain

The one-dimensional XXZ model is studied in the presence of disorder in the Heisenberg Exchange Integral. Recent predictions obtained from renormalization group calculations are investigated numerically using a Lanczos algorithm on chains of up to 18 sites. It is found that in the presence of strong X-Y-symmetric random exchange couplings, a ``random singlet'' phase with quasi-long-range order in the spin-spin correlations persists. As the planar anisotropy is varied, the full zero-temperature phase diagram is obtained and compared with predictions of Doty and Fisher [Phys. Rev. B {\bf 45 }, 2167 (1992)].Comment: 9 pages + 8 plots appended, RevTex, FSU-SCRI-93-98 and ORNL/CCIP/93/1

Dynamical Properties of small Polarons

On the basis of the two-site polaron problem, which we solve by exact diagonalization, we analyse the spectral properties of polaronic systems in view of discerning localized from itinerant polarons and bound polaron pairs from an ensemble of single polarons. The corresponding experimental techniques for that concern photoemission and inverse photoemission spectroscopy. The evolution of the density of states as a function of concentration of charge carriers and strength of the electron-phonon interaction clearly shows the opening up of a gap between single polaronic and bi-polaronic states, in analogy to the Hubbard problem for strongly correlated electron systems. The crossover regime between adiabatic and anti-adiabatic small polarons is triggered by two characteristic time scales: the renormalized electron hopping rate and the renormalized vibrational frequency becoming equal. This crossover regime is then characterized by temporarily alternating self- localization and delocalization of the charge carriers which is accompanied by phase slips in the charge and molecular deformation oscillations and ultimately leads to a dephasing between these two dynamical components of the polaron problem. We visualize these features by a study of the temporal evolution of the charge redistribution and the change in molecular deformations. The spectral and dynamical properties of polarons discussed here are beyond the applicability of the standard Lang Firsov approach to the polaron problem.Comment: 31 pages and 23 figs.(eps), accepted in the Phys. Rev.

Did a submarine landslide contribute to the 2011 Tohoku tsunami?

Many studies have modeled the Tohoku tsunami of March 11, 2011 as being due entirely to slip on an earthquake fault, but the following discrepancies suggest that further research is warranted. (1) Published models of tsunami propagation and coastal impact underpredict the observed runup heights of up to 40 m measured along the coast of the Sanriku district in the northeast part of Honshu Island. (2) Published models cannot reproduce the timing and high-frequency content of tsunami waves recorded at three nearshore buoys off Sanriku, nor the timing and dispersion properties of the waveforms at offshore DART buoy #21418. (3) The rupture centroids obtained by tsunami inversions are biased about 60 km NNE of that obtained by the Global CMT Project. Based on an analysis of seismic and geodetic data, together with recorded tsunami waveforms, we propose that, while the primary source of the tsunami was the vertical displacement of the seafloor due to the earthquake, an additional tsunami source is also required. We infer the location of the proposed additional source based on an analysis of the travel times of higher-frequency tsunami waves observed at nearshore buoys. We further propose that the most likely additional tsunami source was a submarine mass failure (SMF—i.e., a submarine landslide). A comparison of pre- and post-tsunami bathymetric surveys reveals tens of meters of vertical seafloor movement at the proposed SMF location, and a slope stability analysis confirms that the horizontal acceleration from the earthquake was sufficient to trigger an SMF. Forward modeling of the tsunami generated by a combination of the earthquake and the SMF reproduces the recorded on-, near- and offshore tsunami observations well, particularly the high-frequency component of the tsunami waves off Sanriku, which were not well simulated by previous models. The conclusion that a significant part of the 2011 Tohoku tsunami was generated by an SMF source has important implications for estimates of tsunami hazard in the Tohoku region as well as in other tectonically similar regions

An Electrochemical Study of Frustrated Lewis Pairs: A Metal-free Route to Hydrogen Oxidation

[Image: see text] Frustrated Lewis pairs have found many applications in the heterolytic activation of H(2) and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H(2) can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H(2) oxidation by 610 mV (117.7 kJ mol(–1)). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology

Clinical risk factors and atherosclerotic plaque extent to define risk for major events in patients without obstructive coronary artery disease: the long-term coronary computed tomography angiography CONFIRM registry.

AimsIn patients without obstructive coronary artery disease (CAD), we examined the prognostic value of risk factors and atherosclerotic extent.Methods and resultsPatients from the long-term CONFIRM registry without prior CAD and without obstructive (≥50%) stenosis were included. Within the groups of normal coronary computed tomography angiography (CCTA) (N = 1849) and non-obstructive CAD (N = 1698), the prognostic value of traditional clinical risk factors and atherosclerotic extent (segment involvement score, SIS) was assessed with Cox models. Major adverse cardiac events (MACE) were defined as all-cause mortality, non-fatal myocardial infarction, or late revascularization. In total, 3547 patients were included (age 57.9 ± 12.1 years, 57.8% male), experiencing 460 MACE during 5.4 years of follow-up. Age, body mass index, hypertension, and diabetes were the clinical variables associated with increased MACE risk, but the magnitude of risk was higher for CCTA defined atherosclerotic extent; adjusted hazard ratio (HR) for SIS >5 was 3.4 (95% confidence interval [CI] 2.3-4.9) while HR for diabetes and hypertension were 1.7 (95% CI 1.3-2.2) and 1.4 (95% CI 1.1-1.7), respectively. Exclusion of revascularization as endpoint did not modify the results. In normal CCTA, presence of ≥1 traditional risk factors did not worsen prognosis (log-rank P = 0.248), while it did in non-obstructive CAD (log-rank P = 0.025). Adjusted for SIS, hypertension and diabetes predicted MACE risk in non-obstructive CAD, while diabetes did not increase risk in absence of CAD (P-interaction = 0.004).ConclusionAmong patients without obstructive CAD, the extent of CAD provides more prognostic information for MACE than traditional cardiovascular risk factors. An interaction was observed between risk factors and CAD burden, suggesting synergistic effects of both