Enhancement of electrocatalysis through magnetic field effects on mass transport.

Magnetic field effects on electrocatalysis have recently gained attention due to the substantial enhancement of the oxygen evolution reaction (OER) on ferromagnetic catalysts. When detecting an enhanced catalytic activity, the effect of magnetic fields on mass transport must be assessed. In this study, we employ a specifically designed magneto-electrochemical system and non-magnetic electrodes to quantify magnetic field effects. Our findings reveal a marginal enhancement in reactions with high reactant availability, such as the OER, whereas substantial boosts exceeding 50% are observed in diffusion limited reactions, exemplified by the oxygen reduction reaction (ORR). Direct visualization and quantification of the whirling motion of ions under a magnetic field underscore the importance of Lorentz forces acting on the electrolyte ions, and demonstrate that bubbles' movement is a secondary phenomenon. Our results advance the fundamental understanding of magnetic fields in electrocatalysis and unveil new prospects for developing more efficient and sustainable energy conversion technologies.

Erratum: Long-Distance Coherent Propagation of High-Velocity Antiferromagnetic Spin Waves [Phys. Rev. Lett. 130, 096701 (2023)].

This corrects the article DOI: 10.1103/PhysRevLett.130.096701.

Optically Enhanced Solid-State 1H NMR Spectroscopy.

Low sensitivity is the primary limitation to extending nuclear magnetic resonance (NMR) techniques to more advanced chemical and structural studies. Photochemically induced dynamic nuclear polarization (photo-CIDNP) is an NMR hyperpolarization technique where light is used to excite a suitable donor-acceptor system, creating a spin-correlated radical pair whose evolution drives nuclear hyperpolarization. Systems that exhibit photo-CIDNP in solids are not common, and this effect has, up to now, only been observed for 13C and 15N nuclei. However, the low gyromagnetic ratio and natural abundance of these nuclei trap the local hyperpolarization in the vicinity of the chromophore and limit the utility for bulk hyperpolarization. Here, we report the first example of optically enhanced solid-state 1H NMR spectroscopy in the high-field regime. This is achieved via photo-CIDNP of a donor-chromophore-acceptor molecule in a frozen solution at 0.3 T and 85 K, where spontaneous spin diffusion among the abundant strongly coupled 1H nuclei relays polarization through the whole sample, yielding a 16-fold bulk 1H signal enhancement under continuous laser irradiation at 450 nm. These findings enable a new strategy for hyperpolarized NMR beyond the current limits of conventional microwave-driven DNP.

Long-Distance Coherent Propagation of High-Velocity Antiferromagnetic Spin Waves.

We report on coherent propagation of antiferromagnetic (AFM) spin waves over a long distance (∼10 µm) at room temperature in a canted AFM α-Fe_{2}O_{3} owing to the Dzyaloshinskii-Moriya interaction (DMI). Unprecedented high group velocities (up to 22.5 km/s) are characterized by microwave transmission using all-electrical spin wave spectroscopy. We derive analytically AFM spin-wave dispersion in the presence of the DMI which accounts for our experimental results. The AFM spin waves excited by nanometric coplanar waveguides have large wave vectors in the exchange regime and follow a quasilinear dispersion relation. Fitting of experimental data with our theoretical model yields an AFM exchange stiffness length of 1.7 Å. Our results provide key insights on AFM spin dynamics and demonstrate high-speed functionality for AFM magnonics.

Nonlocal Detection of Interlayer Three-Magnon Coupling.

A leading nonlinear effect in magnonics is the interaction that splits a high-frequency magnon into two low-frequency magnons with conserved linear momentum. Here, we report experimental observation of nonlocal three-magnon scattering between spatially separated magnetic systems, viz. a CoFeB nanowire and a yttrium iron garnet (YIG) thin film. Above a certain threshold power of an applied microwave field, a CoFeB Kittel magnon splits into a pair of counterpropagating YIG magnons that induce voltage signals in Pt electrodes on each side, in excellent agreement with model calculations based on the interlayer dipolar interaction. The excited YIG magnon pairs reside mainly in the first excited (n=1) perpendicular standing spin-wave mode. With increasing power, the n=1 magnons successively scatter into nodeless (n=0) magnons through a four-magnon process. Our results demonstrate nonlocal detection of two separately propagating magnons emerging from one common source that may enable quantum entanglement between distant magnons for quantum information applications.

Heterogeneous Overhauser-DNP on 1 H dominated by scalar coupling in aqueous solution.

The Overhauser Dynamic Nuclear Polarization (O-DNP) of 1 H nuclei usually involves a dipolar coupling with the polarizing agent, whereas scalar coupling via hyperfine interactions are more common with 13 C nuclei. Here, we show a scalar-coupling dominated 1 H O-DNP, using polyaniline as a heterogeneous polarizing agent in an aqueous solution.

Blatter-type radicals as polarizing agents for electrochemical overhauser dynamic nuclear polarization.

Overhauser dynamic nuclear polarization (O-DNP) refers to a microwave-assisted process where an unpaired electron's (e.g. a radical) spin polarization is transferred to surrounding nuclei in solution, thus increasing the nuclear magnetic resonance (NMR) signal intensity of a given substance by several orders of magnitude. The presence of the unpaired electrons, which induces relaxation of the resulting hyperpolarized state when the radiation is halted, can be avoided by electrochemically removing the radicals on demand. We report the use of Blatter-type (benzo[e][1,2,4]triazinyl) radicals as polarizing agents, potentially opening the way to highly tunable radicals for electrochemical DNP.

Hyperactivity of the default mode network in schizophrenia and free energy: A dialogue between Freudian theory of psychosis and neuroscience.

The economic conceptualization of Freudian metapsychology, based on an energetics model of the psyche's workings, offers remarkable commonalities with some recent discoveries in neuroscience, notably in the field of neuroenergetics. The pattern of cerebral activity at resting state and the identification of a default mode network (DMN), a network of areas whose activity is detectable at baseline conditions by neuroimaging techniques, offers a promising field of research in the dialogue between psychoanalysis and neuroscience. In this article we study one significant clinical application of this interdisciplinary dialogue by looking at the role of the DMN in the psychopathology of schizophrenia. Anomalies in the functioning of the DMN have been observed in schizophrenia. Studies have evidenced the existence of hyperactivity in this network in schizophrenia patients, particularly among those for whom a positive symptomatology is dominant. These data are particularly interesting when considered from the perspective of the psychoanalytic understanding of the positive symptoms of psychosis, most notably the Freudian hypothesis of delusions as an "attempt at recovery." Combining the data from research in neuroimaging of schizophrenia patients with the Freudian hypothesis, we propose considering the hyperactivity of the DMN as a consequence of a process of massive reassociation of traces occurring in schizophrenia. This is a process that may constitute an attempt at minimizing the excess of free energy present in psychosis. Modern models of active inference and the free energy principle (FEP) may shed some light on these processes.

Long decay length of magnon-polarons in BiFeO3/La0.67Sr0.33MnO3 heterostructures.

Magnons can transfer information in metals and insulators without Joule heating, and therefore are promising for low-power computation. The on-chip magnonics however suffers from high losses due to limited magnon decay length. In metallic thin films, it is typically on the tens of micrometre length scale. Here, we demonstrate an ultra-long magnon decay length of up to one millimetre in multiferroic/ferromagnetic BiFeO3(BFO)/La0.67Sr0.33MnO3(LSMO) heterostructures at room temperature. This decay length is attributed to a magnon-phonon hybridization and is more than two orders of magnitude longer than that of bare metallic LSMO. The long-distance modes have high group velocities of 2.5 km s-1 as detected by time-resolved Brillouin light scattering. Numerical simulations suggest that magnetoelastic coupling via the BFO/LSMO interface hybridizes phonons in BFO with magnons in LSMO to form magnon-polarons. Our results provide a solution to the long-standing issue on magnon decay lengths in metallic magnets and advance the bourgeoning field of hybrid magnonics.

Electrochemical Overhauser dynamic nuclear polarization.

Nuclear Magnetic Resonance (NMR) spectroscopy suffers from low sensitivity due to the low nuclear spin polarization obtained within practically achievable external magnetic fields. Dynamic Nuclear Polarization (DNP) refers to techniques that increase the NMR signal intensity by transferring spin polarization from electrons to the nuclei. Until now, a common method of introducing unpaired electrons to a sample has been to add to it a radical such as TEMPOL or trityl. The alternative we address here is to use electrochemical oxidation and/or reduction of a redox mediator to generate radical species that can be used for DNP. Surprisingly, the potential of electrochemically-generated radicals as a source of hyperpolarization for DNP has not been investigated so far. In this communication, we show the proof of principle of performing an in situ DNP experiment at a low magnetic field in a solution phase, with electrochemically generated methyl viologen cation radicals. Electrochemistry as a source of radicals can offer exciting prospects for DNP. The electrode may be one that generates radicals with a high spin polarization. The concentration of radicals in the sample can be adjusted by changing the duration and magnitude of the applied electrode potential. Removal of the radical from the sample after spin polarization transfer is also possible, thereby increasing the lifetime of the nuclear hyperpolarization.

Author Correction: Record thermopower found in an IrMn-based spintronic stack.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Record thermopower found in an IrMn-based spintronic stack.

The Seebeck effect converts thermal gradients into electricity. As an approach to power technologies in the current Internet-of-Things era, on-chip energy harvesting is highly attractive, and to be effective, demands thin film materials with large Seebeck coefficients. In spintronics, the antiferromagnetic metal IrMn has been used as the pinning layer in magnetic tunnel junctions that form building blocks for magnetic random access memories and magnetic sensors. Spin pumping experiments revealed that IrMn Néel temperature is thickness-dependent and approaches room temperature when the layer is thin. Here, we report that the Seebeck coefficient is maximum at the Néel temperature of IrMn of 0.6 to 4.0 nm in thickness in IrMn-based half magnetic tunnel junctions. We obtain a record Seebeck coefficient 390 (±10) µV K-1 at room temperature. Our results demonstrate that IrMn-based magnetic devices could harvest the heat dissipation for magnetic sensors, thus contributing to the Power-of-Things paradigm.

From the Principle of Inertia to the Death Drive: The Influence of the Second Law of Thermodynamics on the Freudian Theory of the Psychical Apparatus.

In the Freudian theory of the psychical apparatus, the introduction from the 1920s onward of the second drive dualism appears as a major turning point. The idea of a "death drive," first expressed in Beyond the Pleasure Principle (Freud, 1920), is generally considered to be a new concept, one that represents a break with Freud's previous thinking. It has often surprised the scholars because it seemed, at first sight, difficult to reconcile with the idea of the singularity of living organisms within which the psychical functions form an integral part. Our research aims to demonstrate that the theory of the death drive does not represent a complete change in direction for Freud. It is present, in essence, in his earliest work, to the extent that the "principle of inertia" described in 1895 in A Project for a Scientific Psychology (Freud, 1895) can be seen as a precursor to the death drive. Based on a reading of Freud's early formulations of his ideas, we aim to bring to light how certain aporias that seem inherent to the concept of the death drive can be overcome if we consider them in the context of an epistemological model that draws on the paradigms of physics which were conveyed by the Helmholtz School. Namely, we can consider the idea of death drive in reference to the principle of entropy and the laws of thermodynamics.

Spin-dependent charge transfer at chiral electrodes probed by magnetic resonance.

Chirality-induced spin selectivity is evidenced by exciting the spin resonance of radicals in an electrochemical cell where the working electrode is covered with a chiral self-assembled monolayer. Because the electron transfer to and from the paramagnetic radical is spin dependent, the electrochemical current changes at resonance. This electrically-detected magnetic resonance (EDMR) is monitored by a lock-in detection based on electrode voltage modulation, at a frequency that optimizes the sensitivity of the differential conductance to the electrode charge transfer process. The method is validated using p-doped GaAs electrodes in which the conduction band electrons are hyperpolarized by a well-known method of optical spin pumping with circularly polarized light. Gold electrodes covered with peptides consisting of 5 alanine groups (Al5) present a relative current change of up to 5 × 10-5 when the resonance condition is met, corresponding to a spin filtering efficiency between 6 and 19%.

High-Field Liquid-State Dynamic Nuclear Polarization in Microliter Samples.

Nuclear hyperpolarization in the liquid state by dynamic nuclear polarization (DNP) has been of great interest because of its potential use in NMR spectroscopy of small samples of biological and chemical compounds in aqueous media. Liquid state DNP generally requires microwave resonators in order to generate an alternating magnetic field strong enough to saturate electron spins in the solution. As a consequence, the sample size is limited to dimensions of the order of the wavelength, and this restricts the sample volume to less than 100 nL for DNP at 9 T (∼260 GHz). We show here a new approach that overcomes this sample size limitation. Large saturation of electron spins was obtained with a high-power (∼150 W) gyrotron without microwave resonators. Since high power microwaves can cause serious dielectric heating in polar solutions, we designed a planar probe which effectively alleviates dielectric heating. A thin liquid sample of 100 µm of thickness is placed on a block of high thermal conductivity aluminum nitride, with a gold coating that serves both as a ground plane and as a heat sink. A meander or a coil were used for NMR. We performed 1H DNP at 9.2 T (∼260 GHz) and at room temperature with 10 µL of water, a volume that is more than 100× larger than reported so far. The 1H NMR signal is enhanced by a factor of about -10 with 70 W of microwave power. We also demonstrated the liquid state of 31P DNP in fluorobenzene containing triphenylphosphine and obtained an enhancement of ∼200.

Magnetic Contribution to the Seebeck Effect.

The Seebeck effect is derived within the thermodynamics of irreversible processes when the generalized forces contain the magnetic term M ∇ B . This term appears in the formalism when the magnetic field is treated as a state variable. Two subsystems are considered, one representing atomic magnetic moments, and the other, mobile charges carrying a magnetic dipole moment. A magnetic contribution to the Seebeck coefficient is identified, proportional to the logarithmic derivative of the magnetization with respect to temperature. A brief review of experimental data on magneto-thermopower in magnetic metals illustrates this magnetic effect on thermally-driven charge transport.

500-fold enhancement of in situ (13)C liquid state NMR using gyrotron-driven temperature-jump DNP.

A 550-fold increase in the liquid state (13)C NMR signal of a 50µL sample was obtained by first hyperpolarizing the sample at 20K using a gyrotron (260GHz), then, switching its frequency in order to apply 100W for 1.5s so as to melt the sample, finally, turning off the gyrotron to acquire the (13)C NMR signal. The sample stays in its NMR resonator, so the sequence can be repeated with rapid cooling as the entire cryostat stays cold. DNP and thawing of the sample are performed only by the switchable and tunable gyrotron without external devices. Rapid transition from DNP to thawing in one second time scale was necessary especially in order to enhance liquid (1)H NMR signal.

Dynamic nuclear polarization by frequency modulation of a tunable gyrotron of 260GHz.

An increase in Dynamic Nuclear Polarization (DNP) signal intensity is obtained with a tunable gyrotron producing frequency modulation around 260GHz at power levels less than 1W. The sweep rate of frequency modulation can reach 14kHz, and its amplitude is fixed at 50MHz. In water/glycerol glassy ice doped with 40mM TEMPOL, the relative increase in the DNP enhancement was obtained as a function of frequency-sweep rate for several temperatures. A 68 % increase was obtained at 15K, thus giving a DNP enhancement of about 80. By employing λ/4 and λ/8 polarizer mirrors, we transformed the polarization of the microwave beam from linear to circular, and achieved an increase in the enhancement by a factor of about 66% for a given power.

Nuclear polarization by optical pumping in InP:Fe above liquid nitrogen temperature.

Hyperpolarized nuclear spins are observed in optically pumped iron-doped InP from 70K to 140K. (31)P NMR was carried out at 9.28T (159.8MHz) during optical excitation with circularly polarized light, using a laser diode (λ∼830nm) as a source. The enhancement of the nuclear spin polarization by optical pumping at 70K is estimated to be about 34 for those nuclei in the region of the sample absorbing light. This enhancement decreases with increasing temperature. As the direction of the enhanced nuclear spin polarization is found parallel or antiparallel to the travelling direction of the σ(+) or σ(-), the contact hyperfine interaction is dominant compared to the dipolar hyperfine interaction.