Spin coupling around a carbon atom vacancy in graphene

We investigate the details of the electronic structure in the neighborhoods of a carbon atom vacancy in graphene by employing magnetization-constrained density-functional theory on periodic slabs, and spin-exact, multi-reference, second-order perturbation theory on a finite cluster. The picture that emerges is that of two local magnetic moments (one \pi-like and one \sigma-like) decoupled from the \pi- band and coupled to each other. We find that the ground state is a triplet with a planar equilibrium geometry where an apical C atom opposes a pentagonal ring. This state lies ~0.2 eV lower in energy than the open-shell singlet with one spin flipped, which is a bistable system with two equivalent equilibrium lattice configurations (for the apical C atom above or below the lattice plane) and a barrier ~0.1 eV high separating them. Accordingly, a bare carbon-atom vacancy is predicted to be a spin-one paramagnetic species, but spin-half paramagnetism can be accommodated if binding to foreign species, ripples, coupling to a substrate, or doping are taken into account

5kWe+5kWt reformer-PEMFC energy generator from bioethanol first data on the fuel processor from a demonstrative project

A power unit constituted by a reformer section, a H 2 purification section and a fuel cell stack is being tested c/o the Dept. of Physical Chemistry and Electrochemistry of Universit\ue0 degli Studi di Milano, on the basis of a collaboration with HELBIO S.A. Hydrogen and Energy Production Systems, Patras (Greece), supplier of the unit, and some sponsors (Linea Energia S.p.A., Parco Tecnologico Padano and Provincia di Lodi, Italy). The system size allows to co-generate 5 kW e (220 V, 50 Hz a.c.) + 5 kW t (hot water at 65\ub0C) as peak output. Bioethanol, obtainable by different non-food-competitive biomass, is transformed into syngas by a pre-reforming and reforming reactors couple and the reformate is purified from CO to a concentration below 20 ppmv, suitable to feed a proton exchange membrane fuel cell (PEMFC) stack that will be integrated in the fuel processor in a second step of the experimentation. This result is achieved by feeding the reformate to two water gas shift reactors, connected in series and operating at high and low temperature, respectively. CO concentration in the outcoming gas is ca. 0.4 vol% and the final CO removal to meet the specifications is accomplished by two methanation reactors in series. The second methanation step acts merely as a guard, since ca. 15 ppmv of CO are obtained already after the first reactor. The goals of the present project are to test the integrated fuel processor, to check the effectiveness of the proposed technology and to suggest possible adequate improvements

Fighting the curse of dimensionality in first-principles semiclassical calculations : Non-local reference states for large number of dimensions

Semiclassical methods face numerical challenges as the dimensionality of the system increases. In the general context of the theory of differential equations, this is known as the curse of dimensionality. In the present manuscript, we apply the recently-introduced multi-coherent states semiclassical initial value representation (MC-SC-IVR) approach to extend the applicability of first-principles semiclassical calculations. The proposed strategy involves the use of non-local coherent states with the goal of increasing accuracy in the Fourier transforms, and on the other hand, allows for the selection of peaks of different frequencies. The ability to filter desired peaks is important for analyzing the power spectra of complex systems. The MC-SC-IVR approach allows us to solve a 19-dimensional test system and to resolve on-the-fly the power spectra of the formaldehyde molecule with very few classical trajectories

Multiple coherent states semiclassical initial value representation spectra calculations of lateral interactions for CO on Cu(100)

Lateral interactions between carbon monoxide molecules adsorbed on a copper Cu(100) surface are investigated via semiclassical initial value representation (SC-IVR) molecular dynamics. A previous analytical potential is extended to include long-range dipole interactions between coadsorbed molecules and preliminary classical simulations were performed to tune the potential parameters. Then, the spectra for several coadsorbed molecules are calculated using the multiple coherent states approximation of the time-averaging representation of the SC-IVR propagator. Results show strong resonances between coadsorbed molecules as observed by past experiments. Resonances turn into dephasing when isotopical substitutions are performed

Few simple rules governing hydrogenation of graphene dots

We investigated binding of hydrogen atoms to small Polycyclic Aromatic Hydrocarbons (PAHs) - i.e. graphene dots with hydrogen-terminated edges - using density functional theory and correlated wavefunction techniques. We considered a number of PAHs with 3 to 7 hexagonal rings and computed binding energies for most of the symmetry unique sites, along with the minimum energy paths for significant cases. The chosen PAHs are small enough to not present radical character at their edges, yet show a clear preference for adsorption at the edge sites which can be attributed to electronic effects. We show how the results, as obtained at different level of theory, can be rationalized in detail with the help of few simple concepts derivable from a tight-binding model of the $\pi$ electrons

Enhanced Gravity Tractor Technique for Planetary Defense

Given sufficient warning time, Earth-impacting asteroids and comets can be deflected with a variety of different "slow push/pull" techniques. The gravity tractor is one technique that uses the gravitational attraction of a rendezvous spacecraft to the impactor and a low-thrust, high-efficiency propulsion system to provide a gradual velocity change and alter its trajectory. An innovation to this technique, known as the Enhanced Gravity Tractor (EGT), uses mass collected in-situ to augment the mass of the spacecraft, thereby greatly increasing the gravitational force between the objects. The collected material can be a single boulder, multiple boulders, regolith or a combination of different sources. The collected mass would likely range from tens to hundreds of metric tons depending on the size of the impactor and warning time available. Depending on the propulsion system's capability and the mass collected, the EGT approach can reduce the deflection times by a factor of 10 to 50 or more, thus reducing the deflection times of several decades to years or less and overcoming the main criticism of the traditional gravity tractor approach. Additionally, multiple spacecraft can orbit the target in formation to provide the necessary velocity change and further reduce the time needed by the EGT technique to divert hazardous asteroids and comets. The robotic segment of NASA's Asteroid Redirect Mission (ARM) will collect a multi-ton boulder from the surface of a large Near-Earth Asteroid (NEA) and will provide the first ever demonstration of the EGT technique and validate one method of collecting in-situ mass on an asteroid of hazardous size

Multiple coherent states for first-principles semiclassical initial value representation molecular dynamics

A multiple coherent states implementation of the semiclassical approximation is introduced and employed to obtain the power spectra with a few classical trajectories. The method is integrated with the time-averaging semiclassical initial value representation to successfully reproduce anharmonicity and Fermi resonance splittings at a level of accuracy comparable to semiclassical simulations of thousands of trajectories. The method is tested on two different model systems with analytical potentials and implemented in conjunction with the first-principles molecular dynamics scheme to obtain the power spectrum for the carbon dioxide molecule

4 th IAA Planetary Defense Conference -PDC

Abstract Given sufficient warning time, Earth-impacting asteroids and comets can be deflected with a variety of different "slow push/pull" techniques. The gravity tractor is one technique that uses the gravitational attraction of a rendezvous spacecraft to the impactor and a low-thrust, high-efficiency propulsion system to provide a gradual velocity change and alter its trajectory. An innovation to this technique, known as the Enhanced Gravity Tractor (EGT), uses mass collected in-situ to augment the mass of the spacecraft, thereby greatly increasing the gravitational force between the objects. The collected material can be a single boulder, multiple boulders, regolith or a combination of different sources. The collected mass would likely range from tens to hundreds of metric tons depending on the size of the impactor and warning time available. Depending on the propulsion system's capability and the mass collected, the EGT approach can reduce the deflection times by a factor of 10 to 50 or more, thus reducing the deflection times of several decades to years or less and overcoming the main criticism of the traditional gravity tractor approach. Additionally, multiple spacecraft can orbit the target in formation to provide the necessary velocity change and further reduce the time needed by the EGT technique to divert hazardous asteroids and comets. The robotic segment of NASA's Asteroid Redirect Mission (ARM) will collect a multi-ton boulder from the surface of a large Near-Earth Asteroid (NEA) and will provide the first ever demonstration of the EGT technique and validate one method of collecting in-situ mass on an asteroid of hazardous size.

TDP-43 oligomerization and RNA binding are codependent but their loss elicits distinct pathologies

Aggregation of the RNA-binding protein TDP-43 is the main common neuropathological feature of TDP-43 proteinopathies. In physiological conditions, TDP-43 is predominantly nuclear and contained in biomolecular condensates formed via liquid-liquid phase separation (LLPS). However, in disease, TDP-43 is depleted from these compartments and forms cytoplasmic or, sometimes, intranuclear inclusions. How TDP-43 transitions from physiological to pathological states remains poorly understood. Here, we show that self-oligomerization and RNA binding cooperatively govern TDP-43 stability, functionality, LLPS and cellular localization. Importantly, our data reveal that TDP-43 oligomerization is connected to, and conformationally modulated by, RNA binding. Mimicking the impaired proteasomal activity observed in patients, we found that TDP-43 forms nuclear aggregates via LLPS and cytoplasmic aggregates via aggresome formation. The favored aggregation pathway depended on the TDP-43 state –monomeric/oligomeric, RNA-bound/-unbound– and the subcellular environment –nucleus/cytoplasm. Our work unravels the origins of heterogeneous pathological species occurring in TDP-43 proteinopathies