Challenges in the simulation of large scale, medium exposed, inorganic nanotubes

Prompted by growing environmental and energy concerns, increasing research is dedicated to the development of technologies capable of sustainably converting sunlight into commercially viable forms of energy such as chemical fuels. Crucial to this energy conversion is the availability of materials, photo-catalysts (PCs), capable of promoting redox chemistry following absorption of light. Since the macroscopic efficiency of PCs is governed by the atomistic details of the PCs interfaces with media and reactants, increasingly large efforts have been dedicated to the characterization and understanding of these interfaces, also by mean of first principle simulations. In this context, we present a theoretical investigation of a rapidly growing class of onedimensional nanomaterial, Imogolite nanotubes (Imo NTs), whose potential for photocatalysis has so far been overlooked. The first Chapter of the Thesis provides an overview of the current state of the art for research in PCs, and the theoretical framework needed for atomic-scale understanding and informed development of PCs. The computational underpinning of the research carried out for this Thesis, namely Density Functional Theory (DFT) and its linear-scaling (LS) implementation in the ONETEP program is presented and discussed in Chapter 2. Ahead of presentation of the results of my original research, a small literature review on Imo NTs is provided in Chapter 3. Chapter 4 illustrates the applicability of LS-DFT to Imo NTs and, by mean of detailed benchmarking, sets best practice for simulations of these systems. The potential of Imo NTs as (co-)PCs is explored in Chapter 5, where an extensive study of the structure, wall-polarization, absolute band-alignment, band-separation, and optical properties of several Imo NTs is presented and discussed. The simulations suggest possible profitable use of Imo NTs for both photo-reduction and hole-scavenging purposes. The occurrence of (near-)UV charge-transfer excitations is also observed, which may be effective for electron-hole separation and enhanced photo-catalytic performances. Finally, the effects of the NTs’ wall-polarization on the absolute alignment of electron and hole acceptor states of interacting water (H2O) molecules are quantified and discussed. Chapter 6 reports an extensive study of defects in Imo NTs. Electronic and optical characterization of the defective Imo NTs suggests energetically favourable separation of photo-generated electrons and holes via relaxation to different defect-sites, with the ensuing possibility of defect-centred photo-redox activity in defective Imo NTs. The Thesis ends with the investigation of termination effects in Imo NTs. Chapter 7 presents results on the structural, electronic and optical characterization of representative finite Imo NTs models capable of simultaneous description of the NT-ends and bulk-like NT-core. The simulations reveal the presence of longitudinal band-bending and of NT core-end bandsseparations, which in turn suggests advantageous relaxation mechanisms for photo-generated e*-h pairs along the NT axis, to the potential benefit of Imo NTs photo-catalytic reactivity

Effects of surface chemical modifications on the adhesion of metallic interfaces. An high-throughput analysis

Chemical interactions between two surfaces in contact play a crucial role in determining the mechanical and tribological behavior of solid interfaces. These interactions can be quantified via adhesion energy, that is a measure of the strength by which two surfaces bind together. Several works in literature report how the presence of chemisorbed atoms at homo- and heterogeneous solid-solid interfaces drastically change their proprieties. A precise evaluation of how different species at solid contacts modulates their adhesion would be extremely beneficial for a range of different technological fields: from metallurgy to nuclear fusion. In this work we have used and high-throughput approach to systematically explore the effects of the presence of non-metallic elements, at different concentrations, on the adsorption and adhesion energies of different homogeneous metallic interfaces. Together with the databases for the adsorption and the adhesion energies, we calculated several other properties such as the charge transferred at the interface, the d-band edge shift for the substrate the Bond order and the interfacial density redistribution for the hundreds of systems analyzed. These values were used to define different trends with respect to chemical and concentration parameters that could be useful for the development of engineered interfaces with selected properties. In particular we noticed how the substrate with low filling of d-band are the most prone to adsorb ad-atoms and how the adsorption of almost all non-metallic elements decreases the adhesion energy of solid interfaces, particularly in the case of Fluorine. Carbon and Boron were the only two ad-atoms species that showed an opposite trend increasing the adhesion energy instead

Chemically selective alternatives to photoferroelectrics for polarization-enhanced photocatalysis: the untapped potential of hybrid inorganic nanotubes

Linear-scaling density functional theory simulation of methylated imogolite nanotubes (NTs) elucidates the interplay between wall-polarization, bands separation, charge-transfer excitation, and tunable electrostatics inside and outside the NT-cavity. The results suggest that integration of polarization-enhanced selective photocatalysis and chemical separation into one overall dipole-free material should be possible. Strategies are proposed to increase the NT polarization for maximally enhanced electron–hole separation

A Hybrid Magneto-Optic Capacitive Memory with Picosecond Writing Time

The long-term future of information storage requires the use of sustainable nanomaterials in architectures operating at high frequencies. Interfaces can play a key role in this pursuit via emergent functionalities that break out from conventional operation methods. Here, spin-filtering effects and photocurrents are combined at metal-molecular-oxide junctions in a hybrid magneto-capacitive memory. Light exposure of metal-fullerene-metal oxide devices results in spin-polarized charge trapping and the formation of a magnetic interface. Because the magnetism is generated by a photocurrent, the writing time is determined by exciton formation and splitting, electron hopping, and spin-dependent trapping. Transient absorption spectroscopy measurements show changes in the electronic states as a function of the magnetic history of the device within picoseconds of the optical pumping. The stored information is read using time-resolved scanning magneto optic Kerr effect measurements during microwave irradiation. The emergence of a magnetic interface in the picosecond timescale opens new paths of research to design hybrid magneto-optic structures operating at high frequencies for sensing, computing, and information storage

Structural resolution of inorganic nanotubes with complex stoichiometry.

Determination of the atomic structure of inorganic single-walled nanotubes with complex stoichiometry remains elusive due to the too many atomic coordinates to be fitted with respect to X-ray diffractograms inherently exhibiting rather broad features. Here we introduce a methodology to reduce the number of fitted variables and enable resolution of the atomic structure for inorganic nanotubes with complex stoichiometry. We apply it to recently synthesized methylated aluminosilicate and aluminogermanate imogolite nanotubes of nominal composition (OH)3Al2O3Si(Ge)CH3. Fitting of X-ray scattering diagrams, supported by Density Functional Theory simulations, reveals an unexpected rolling mode for these systems. The transferability of the approach opens up for improved understanding of structure-property relationships of inorganic nanotubes to the benefit of fundamental and applicative research in these systems

Short hydrogen bonds enhance nonaromatic protein-related fluorescence.

Fluorescence in biological systems is usually associated with the presence of aromatic groups. Here, by employing a combined experimental and computational approach, we show that specific hydrogen bond networks can significantly affect fluorescence. In particular, we reveal that the single amino acid L-glutamine, by undergoing a chemical transformation leading to the formation of a short hydrogen bond, displays optical properties that are significantly enhanced compared with L-glutamine itself. Ab initio molecular dynamics simulations highlight that these short hydrogen bonds prevent the appearance of a conical intersection between the excited and the ground states and thereby significantly decrease nonradiative transition probabilities. Our findings open the door to the design of new photoactive materials with biophotonic applications

Short hydrogen bonds enhance nonaromatic protein-related fluorescence.

Fluorescence in biological systems is usually associated with the presence of aromatic groups. Here, by employing a combined experimental and computational approach, we show that specific hydrogen bond networks can significantly affect fluorescence. In particular, we reveal that the single amino acid L-glutamine, by undergoing a chemical transformation leading to the formation of a short hydrogen bond, displays optical properties that are significantly enhanced compared with L-glutamine itself. Ab initio molecular dynamics simulations highlight that these short hydrogen bonds prevent the appearance of a conical intersection between the excited and the ground states and thereby significantly decrease nonradiative transition probabilities. Our findings open the door to the design of new photoactive materials with biophotonic applications

Enhanced Spin-Orbit Coupling in Heavy Metals via Molecular Coupling

5d metals are used in electronics because of their high spin–orbit coupling (SOC) leading to efficient spin-electric conversion. When C60 is grown on a metal, the electronic structure is altered due to hybridization and charge transfer. In this work, we measure the spin Hall magnetoresistance for Pt/C60 and Ta/C60, finding that they are up to a factor of 6 higher than those for pristine metals, indicating a 20–60% increase in the spin Hall angle. At low fields of 1–30 mT, the presence of C60 increased the anisotropic magnetoresistance by up to 700%. Our measurements are supported by noncollinear density functional theory calculations, which predict a significant SOC enhancement by C60 that penetrates through the Pt layer, concomitant with trends in the magnetic moment of transport electrons acquired via SOC and symmetry breaking. The charge transfer and hybridization between the metal and C60 can be controlled by gating, so our results indicate the possibility of dynamically modifying the SOC of thin metals using molecular layers. This could be exploited in spin-transfer torque memories and pure spin current circuits

History of migraine and volume of brain infarcts: The italian project on stroke at young age (IPSYS)

BACKGROUND AND PURPOSE: Migraine has been shown to increase cerebral excitability, promote rapid infarct expansion into tissue with perfusion deficits, and result in larger infarcts in animal models of focal cerebral ischemia. Whether these effects occur in humans has never been properly investigated. METHODS: In a series of consecutive patients with acute ischemic stroke, enrolled in the setting of the Italian Project on Stroke at Young Age, we assessed acute as well as chronic infarct volumes by volumetric magnetic resonance imaging, and compared these among different subgroups identified by migraine status. RESULTS: A cohort of 591 patients (male, 53.8%; mean age, 37.5±6.4 years) qualified for the analysis. Migraineurs had larger acute infarcts than non-migraineurs (median, 5.9 cm3 [interquartile range (IQR), 1.4 to 15.5] vs. 2.6 cm3 [IQR, 0.8 to 10.1], P<0.001), and the largest volumes were observed in patients with migraine with aura (median, 9.0 cm3 [IQR, 3.4 to 16.6]). In a linear regression model, migraine was an independent predictor of increased log (acute infarct volumes) (median ratio [MR], 1.64; 95% confidence interval [CI], 1.22 to 2.20), an effect that was more prominent for migraine with aura (MR, 2.92; 95% CI, 1.88 to 4.54). CONCLUSION: s These findings reinforce the experimental observation of larger acute cerebral infarcts in migraineurs, extend animal data to human disease, and support the hypothesis of increased vulnerability to ischemic brain injury in people suffering migraine

Exploring fusion-reactor physics with high-power electron cyclotron resonance heating on ASDEX Upgrade

The electron cyclotron resonance heating (ECRH) system of the ASDEX Upgrade tokomak has been upgraded over the last 15 years from a 2MW, 2 s, 140 GHz system to an 8MW, 10 s, dual frequency system (105/140 GHz). The power exceeds the L/H power threshold by at least a factor of two, even for high densities, and roughly equals the installed ion cyclotron range of frequencies power. The power of both wave heating systems together (>10MW in the plasma) is about half of the available neutral beam injection (NBI) power, allowing significant variations of torque input, of the shape of the heating profile and of Qe/Qi, even at high heating power. For applications at a low magnetic field an X3-heating scheme is routinely in use. Such a scenario is now also forseen for ITER to study the first H-modes at one third of the full field. This versatile system allows one to address important issues fundamental to a fusion reactor: H-mode operation with dominant electron heating, accessing low collisionalities in full metal devices (also related to suppression of edge localized modes with resonant magnetic perturbations), influence of Te/Ti and rotational shear on transport, and dependence of impurity accumulation on heating profiles. Experiments on all these subjects have been carried out over the last few years and will be presented in this contribution. The adjustable localized current drive capability of ECRH allows dedicated variations of the shape of the q-profile and the study of their influence on non-inductive tokamak operation (so far at q$_{95}$>5.3). The ultimate goal of these experiments is to use the experimental findings to refine theoretical models such that they allow a reliable design of operational schemes for reactor size devices. In this respect, recent studies comparing a quasi-linear approach (TGLF) with fully non-linear modeling (GENE) of non-inductive high-beta plasmas will be reported