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Abstract: Titanium borates show promising hydrogen storage characteristics. Structural relaxation around individual hydrogen atoms and the binding energies are studied by means of the density functional theory methods for a number of hydrogenated TiB2 , TiB and Ti2B structures. Starting with the possible symmetric hydrogen sites a random structure searching has been performed, in addition to locate all energetically stable adsorption sites. It is shown that for the three bulk compounds considered, the lowest binding energies are obtained for TiB2 (in the 0.3–1.8 eV range), the largest for Ti2B (in the 3.9–4.7 eV range), while for TiB they are intermediate (in the 2.8–3.5 eV range). Calculations performed on hydrogenated Ti2B result in two energetically stable sites for two different starting environments, suggesting a possible soft mode solution. [Copyright &y& Elsevier]

Abstract: Charge density wave (CDW) ordering in the prototypical low-dimensional compound NbSe3 is reconsidered. It is shown that the model with two incommensurate modulations, and , localized on type-III and type-I bi-capped trigonal prismatic columns, does not explain details, revealed by various microscopic methods. An alternative explanation, based on the existence of modulated layered nano-domains below both CDW onset temperatures, is suggested. It accounts for the presence of the modulation in the STM images recorded above the CDW transition and for the absence of satellites in the corresponding diffraction patterns. The long periodic modulation, detected by LT STM, is attributed to a beating between the two CDWs, centered on adjacent columns of the same type. Such pairs of alternatively modulated columns represent the basic modulation units, ordered into nano-domains. [ABSTRACT FROM AUTHOR]

We review the features of the charge density wave (CDW) conductor NbS3 (phase II) and include several additional results from transport, compositional, and structural studies. Particularly, we highlight three central results: (1) In addition to the previously reported CDW transitions at TP1=360K and TP2=150K, a third CDW transition occurs at a much higher temperature TP0620-650K; evidence for the nonlinear conductivity of this CDW is presented. (2) We show that the CDW associated with the TP2 transition arises from S vacancies acting as donors. Such a CDW transition has not been observed before. (3) We demonstrate the exceptional coherence of the TP1 CDW at room temperature. The effects of uniaxial strain on the CDW transition temperature and transport are reported. [ABSTRACT FROM AUTHOR]

We present an efficient strategy for on-surface engineering of organic metal-free supramolecular complexes with long-term spin protection. By vacuum deposition of azafullerene (C 59 N • ) monomers on a pre-deposited template layer of [10]cycloparaphenylene ([10]CPP) nanohoops on Au(111) surface we exploit the molecular shape matching between the C 59 N • and [10]CPP for the azafullerene encapsulation with nanohoops in a guest-host complexation geometry. C 59 N • ⊂[10]CPP supramolecular complexes self-assemble into an extended two-dimensional hexagonal lattice yielding a high density network of stable spin-1/2 radicals. We find compelling evidence for electronic coupling between the guest C 59 N • and the host [10]CPP in supramolecular species. At the same time, [10]CPP effectively protects the radical state of encapsulated azafullerenes against dimerization and inhibits C 59 N • coupling to the Au substrate. Azafullerene encapsulation by nanohoops represents a viable realization of molecular spin protection while simultaneously demonstrating exceptional self-assembling properties by which large-scale 2D architectures of molecular spins can be realized., Competing Interests: Competing interests: The authors declare no competing interests., (© 2024. The Author(s).)

We deposit azafullerene C 59 N • radicals in a vacuum on the Au(111) surface for layer thicknesses between 0.35 and 2.1 monolayers (ML). The layers are characterized using X-ray photoemission (XPS) and X-ray absorption fine structure (NEXAFS) spectroscopy, low-temperature scanning tunneling microscopy (STM), and by density functional calculations (DFT). The singly unoccupied C 59 N orbital (SUMO) has been identified in the N 1s NEXAFS/XPS spectra of C 59 N layers as a spectroscopic fingerprint of the molecular radical state. At low molecular coverages (up to 1 ML), films of monomeric C 59 N are stabilized with the nonbonded carbon orbital neighboring the nitrogen oriented toward the Au substrate, whereas in-plane intermolecular coupling into diamagnetic (C 59 N) 2 dimers takes over toward the completion of the second layer. By following the C 59 N • SUMO peak intensity with increasing molecular coverage, we identify an intermediate high-spin-density phase between 1 and 2 ML, where uncoupled C 59 N • monomers in the second layer with pronounced radical character are formed. We argue that the C 59 N • radical stabilization of this supramonolayer phase of monomers is achieved by suppressed coupling to the substrate. This results from molecular isolation on top of the passivating azafullerene contact layer, which can be explored for molecular radical state stabilization and positioning on solid substrates.

In an attempt to incorporate tin (Sn) into high-entropy alloys composed of refractory metals Hf, Nb, Ti and Zr with the addition of 3 d transition metals Cu, Fe, and Ni, we synthesized a series of alloys in the system HfTiZrSn M ( M = Cu, Fe, Nb, Ni). The alloys were characterized crystallographically, microstructurally, and compositionally, and their physical properties were determined, with the emphasis on superconductivity. All Sn-containing alloys are multi-phase mixtures of intermetallic compounds (in most cases four). A common feature of the alloys is a microstructure of large crystalline grains of a hexagonal (Hf, Ti, Zr) 5 Sn 3 partially ordered phase embedded in a matrix that also contains many small inclusions. In the HfTiZrSnCu alloy, some Cu is also incorporated into the grains. Based on the electrical resistivity, specific heat, and magnetization measurements, a superconducting (SC) state was observed in the HfTiZr, HfTiZrSn, HfTiZrSnNi, and HfTiZrSnNb alloys. The HfTiZrSnFe alloy shows a partial SC transition, whereas the HfTiZrSnCu alloy is non-superconducting. All SC alloys are type II superconductors and belong to the Anderson class of "dirty" superconductors.

We used a 16-channel e-nose demonstrator based on micro-capacitive sensors with functionalized surfaces to measure the response of 30 different sensors to the vapours from 11 different substances, including the explosives 1,3,5-trinitro-1,3,5-triazinane (RDX), 1-methyl-2,4-dinitrobenzene (DNT) and 2-methyl-1,3,5-trinitrobenzene (TNT). A classification model was developed using the Random Forest machine-learning algorithm and trained the models on a set of signals, where the concentration and flow of a selected single vapour were varied independently. It is demonstrated that our classification models are successful in recognizing the signal pattern of different sets of substances. An excellent accuracy of 96% was achieved for identifying the explosives from among the other substances. These experiments clearly demonstrate that the silane monolayers used in our sensors as receptor layers are particularly well suited to selecting and recognizing TNT and similar types of explosives from among other substances.

Good chemical selectivity of sensors for detecting vapour traces of targeted molecules is vital to reliable detection systems for explosives and other harmful materials. We present the design, construction and measurements of the electronic response of a 16 channel electronic nose based on 16 differential microcapacitors, which were surface-functionalized by different silanes. The e-nose detects less than 1 molecule of TNT out of 10 +12 N₂ molecules in a carrier gas in 1 s. Differently silanized sensors give different responses to different molecules. Electronic responses are presented for TNT, RDX, DNT, H₂S, HCN, FeS, NH₃, propane, methanol, acetone, ethanol, methane, toluene and water. We consider the number density of these molecules and find that silane surfaces show extreme affinity for attracting molecules of TNT, DNT and RDX. The probability to bind these molecules and form a surface-adsorbate is typically 10 +7 times larger than the probability to bind water molecules, for example. We present a matrix of responses of differently functionalized microcapacitors and we propose that chemical selectivity of multichannel e-nose could be enhanced by using artificial intelligence deep learning methods., Competing Interests: Authors declare no conflicts of interest.

It is shown that tiling in icosahedral quasicrystals can also be properly described by cyclic twinning at the unit cell level. The twinning operation is applied on the primitive prolate golden rhombohedra, which can be considered a result of a distorted face-centered cubic parent structure. The shape of the rhombohedra is determined by an exact space filling, resembling the forbidden five-fold rotational symmetry. Stacking of clusters, formed around multiply twinned rhombic hexecontahedra, keeps the rhombohedra of adjacent clusters in discrete relationships. Thus periodicities, interrelated as members of a Fibonacci series, are formed. The intergrown twins form no obvious twin boundaries and fill the space in combination with the oblate golden rhombohedra, formed between clusters in contact. Simulated diffraction patterns of the multiply twinned rhombohedra and the Fourier transform of an extended model structure are in full accord with the experimental diffraction patterns and can be indexed by means of three-dimensional crystallography. The alternative approach is fully compatible to the rather complicated descriptions in a hyper-space.

The article offers a comparison of the sensitivities for vapour trace detection of Trinitrotoluene (TNT) explosives of two different sensor systems: a chemo-mechanical sensor based on chemically modified Atomic Force Microscope (AFM) cantilevers based on Micro Electro Mechanical System (MEMS) technology with optical detection (CMO), and a miniature system based on capacitive detection of chemically functionalized planar capacitors with interdigitated electrodes with a comb-like structure with electronic detection (CE). In both cases (either CMO or CE), the sensor surfaces are chemically functionalized with a layer of APhS (trimethoxyphenylsilane) molecules, which give the strongest sensor response for TNT. The construction and calibration of a vapour generator is also presented. The measurements of the sensor response to TNT are performed under equal conditions for both systems, and the results show that CE system with ultrasensitive electronics is far superior to optical detection using MEMS. Using CMO system, we can detect 300 molecules of TNT in 10(+12) molecules of N2 carrier gas, whereas the CE system can detect three molecules of TNT in 10(+12) molecules of carrier N2.

The real crystal structure of the (NbSe4)(10/3)I charge density wave (CDW) compound is studied by simulation of the X-ray diffuse scattering. The average structure of the low-temperature twinned phase is determined and the phase transition is attributed to the formation of a CDW. The diffuse streaking, present in X-ray diffraction patterns above and below the transition at T = 282 K, is shown to be a projection of diffuse concentric rings perpendicular to the c* direction. The simulated patterns, based on a mismatch model between infinite NbSe4 chains, correlated by I atoms, are in good accordance with the experimental patterns. In addition to the experiments, the electronic properties of the high- and the low-temperature phases are calculated with the extended Hückel tight-binding method. The Fermi surfaces of the average structures above and below the phase transition appear very similar. Their shapes support a nesting instability and a CDW formation. The weak incommensurate CDW satellites, present below the phase transition, are at 100 K properly described by a modulation wavevector q = [0.06 (1), 0, 0.55 (1)].