Search

The demand for fast-charging metal-ion batteries underlines the importance of anodes that work at high currents with no risk of dendrite formation. NiBTA, a one-dimensional Ni-based polymer derived from benzenetetramine (BTA), is a recently proposed promising material for safe fast-charging batteries. However, its charge-discharge mechanisms remained unclear and controversial. Here we solve the controversies by providing the first rigorous study using a combination of advanced theoretical and experimental techniques, including

Starting from recent advances in the first-principles modeling of polarons, variational polaron equations in the strong-coupling adiabatic approximation are formulated in Bloch space. In this framework, polaron formation energy as well as individual electron, phonon and electron-phonon contributions are obtained. We suggest an efficient gradient-based optimization algorithm and apply these equations to the generalized Fr\"ohlich model with anisotropic non-degenerate electronic bands, both in two- and three-dimensional cases. The effect of the divergence of Fr\"ohlich electron-phonon matrix elements at $\Gamma$-point is treated analytically, improving the convergence with respect to the sampling in reciprocal space. The whole methodology is validated by obtaining the known asymptotic solution of the standard Fr\"ohlich model in isotropic scenario and also by comparing our results with the Gaussian ansatz approach, showing the difference between the numerically exact and Gaussian trial wavefunctions. Additionally, decomposition of the energy into individual terms allows one to recover the Pekar's 1:2:3:4 theorem, which is shown to be valid even in the anisotropic case. We expect that the improvements in the formalism and numerical implementation will be applicable beyond the large polaron hypothesis inherent to Fr\"ohlich model., Comment: 14 pages, 5 figures

Intermolecular hydrogen bonds impede long-range (anti-)ferroelectric order of water. We confine H2O molecules in nanosized cages formed by ions of a dielectric crystal. Arranging them in channels at a distance of ~5 Å with an interchannel separation of ~10 Å prevents the formation of hydrogen networks while electric dipole-dipole interactions remain effective. Here, we present measurements of the temperature-dependent dielectric permittivity, pyrocurrent, electric polarization and specific heat that indicate an order-disorder ferroelectric phase transition at T0 ≈ 3 K in the water dipolar lattice. Ab initio molecular dynamics and classical Monte Carlo simulations reveal that at low temperatures the water molecules form ferroelectric domains in the ab-plane that order antiferroelectrically along the channel direction. This way we achieve the long-standing goal of arranging water molecules in polar order. This is not only of high relevance in various natural systems but might open an avenue towards future applications in biocompatible nanoelectronics., Despite the apparent simplicity of a H2O molecule, the mutual ferroelectric ordering of the molecules is unresolved. Here, the authors realize a macroscopic ferroelectric phase transition in a network of dipole-dipole coupled water molecules located in nanopores of gemstone.

One of the major challenges in the field of organic photovoltaics is associated with high-throughput manufacturing of efficient and stable organic solar cells. Practical realization of technologies for production of large-area organic solar cells requires the development of novel materials with a defined combination of properties ensuring sufficient reliability and scalability of the process in addition to good efficiency and operation stability of the devices. In this work, we designed two novel polymers comprising thiazolothiazole units and investigated their performance as absorber materials for organic solar cells and modules. Optimized small-area solar cells based on P1/[70]PCBM ([6,6]-phenyl-C71-butyric acid methyl ester) blends exhibited promising power conversion efficiency (PCE) of 7.5%, while larger area modules fabricated using slot die coating showed encouraging PCE of 4.2%. Additionally, the fabricated devices showed promising outdoor stability maintaining 60–70% of the initial efficiency after 20 sun days being exposed to natural sunlight at the Negev desert. The obtained results feature the designed polymer P1 as a promising absorber material for a large-scale production of organic solar cells under ambient conditions.

The change in optical properties of an organic semiconductors upon forming adducts with inexpensive small molecules is attractive in organic electronics. We focus on the adducts of conjugated molecules and Lewis acids (CM-LA), formed by the partial electron transfer from a CM containing a Lewis basic site to an LA such as BF3 and B(C6F5)3. The resulting adducts showed intriguing optoelectronic properties, including a red-shift in optical transitions and an increase in charge carrier density compared to the parent conjugated molecules. In this work, we combine electronic structure modelling and machine learning (ML) to quantify, analyze and predict the electron transfers and red-shifts of the adducts from chemical structures. For ML model, we utilize DFT-calculated electron transfers and redshifts and molecular descriptors readily calculated from molecular structures. Our work can help researchers in other fields in predicting fundamental properties from molecular structures.

We report the first-principles study of small polarons in the most stable two-dimensional pnictogen allotropes: blue and black phosphorene and arsenene. While both cations and anions of small hydrogen-passivated clusters show charge localization and local lattice distortions, only the hole polaron in the blue allotrope is stable in the infinite size cluster limit. The adiabatic polaron relaxation energy is found to be 0.1 eV for phosphorene and 0.15 eV for arsenene. The polaron is localized on lone-pair orbitals with half of the extra charge distributed among 13 atoms. In the blue phosphorene, these orbitals form the valence band's top with a relatively flat band dispersion. However, in the black phosphorene, lone-pair orbitals hybridize with bonding orbitals, which explains the difference in hole localization strength between the two topologically equivalent allotropes. The polaron's adiabatic barriers for motion are small compared to the most strongly coupled phonon frequency, implying the polaron barrierless motion.

High ionic conductivity is a prerequisite requirement for materials used in monovalent metal-ion rechargeable batteries. The extensive search of new electrode materials for Na-ion and K-ion monovalent metal-ion batteries requires a deep understanding of structural and chemical details of cation migration through the crystal lattice. In the paper, we consider three classes of transition metal oxide and phosphate cathode materials: AMn2O4 spinels, AMPO4 olivines and AVPO4F tavorites (A = Li, Na, K, □ ; M = Fe, Mn), used for pragmatic applications for secondary (rechargeable) batteries. Herein we examine Na+ and K+ migration characteristics in comparison with that of Li+ by means of DFT+U, local energy calculations, empirical potentials, and bond valence energy landscape (BVEL). It is found that despite larger radii of Na+ and K+, the migration barriers are comparable with that of Li+. In several cases, we reveal that the migration barrier of K+ can be even lower than that of Li+. This behavior is explained through the interplay of site and lattice energies during cation migration. For automation of screening of migration properties via DFT calculations, a new Python-based framework (SIMAN) is developed and benchmarked across three cathode materials structures.

We systematically study low-energy crystalline polymorphs of the archetypal conjugated polymer, regioregular poly-3-hexylthiophene (rr-P3HT) using the best available density functional theory methods benchmarked against the ab initio coupled cluster method. A comprehensive conformational search is performed for two-dimensional π-stacks being the most rigid structural unit of bulk P3HT. We have identified a number of nearly isoenergetic polymorphs below the energy level of room-temperature amorphous structures and well below the energy of optimized best-fit experimental models. Classical molecular dynamics simulations show that these crystals retain their structure at least at 200 K. At room temperature, although the conjugated backbone of the π-stack remains ordered, aliphatic side chains are melted, transforming from low-energy folded conformations to high-entropy fully unfolded structures. Our study shows that P3HT is a statistically frustrated system with multiple competing interactions, which complica...

Using the orthorhombic layered Na2FePO4F cathode material as a model system we identify the bonding of the alkali metal cations to the semilabile oxygen atoms as an important factor affecting electrochemical activity of alkali cations in polyanion structures. The semilabile oxygens, bonded to the P and alkali cations, but not included into the FeO4F2 octahedra, experience severe undercoordination upon alkali cation deintercalation, causing an energy penalty for removing the alkali cations located in the proximity of such semilabile oxygens. Desodiation of Na2FePO4F proceeds through a two-phase mechanism in the Na-ion cell with a formation of an intermediate monoclinic Na1.55FePO4F phase with coupled Na/vacancy and Fe2+/Fe3+ charge ordering at 50% state of charge. In contrast, desodiation of Na2FePO4F in the Li-ion cell demonstrates a sloping charge profile suggesting a solid solution mechanism without formation of a charge-ordered intermediate phase. A combination of a comprehensive crystallographic study...

In this paper, we report on a novel RbVPO4F fluoride phosphate, which adopts the KTiOPO4 (KTP) type structure and complements the AVPO4F (A = alkali metal) family of positive electrode (cathode) materials for metal-ion batteries. RbVPO4F was synthesized via a freeze-drying assisted solid-state route and characterized via structural, computational and electrochemical methods. RbVPO4F represents the first example of reversible electrochemical Rb+ de/insertion in a crystalline oxypolyanionic framework. The electrochemical measurements on RbVPO4F in a three-electrode cell configuration in RbClO4-saturated propylene carbonate (PC) electrolyte revealed that the material exhibits reversible Rb+ de/insertion within the 0.4–1.3 V vs. Ag+/Ag potential range (∼3.9–4.8 V vs. K+/K) displaying rather high diffusion coefficients of (0.3–1.0) × 10−11 cm2 s−1 comparable to those of K+ in KVPO4F that supports reasonably fast ionic mobility in the KTP structure despite the large ionic radius of the Rb+ ions. The energy barriers of Rb+ ion transport are exceptionally low not exceeding 0.2 eV along the c-axis and correlating well with diffusion coefficients estimated using the DFT+U-NEB methodology and with the experimentally determined transport properties. These results suggest a new paradigm for the development of materials that support many monovalent ion reversible de/insertion processes in a single prototypical structural oxypolyanionic framework.

In this work, we provide a structural and computational investigation of the Li2CoPO4F high-voltage cathode material by means of neutron powder diffraction (SG Pnma, a = 10.4528(2) A, b = 6.38667(10) A, c = 10.8764(2) A, RF = 0.0145), crystal chemistry approaches (Voronoi–Dirichlet partitioning and bond valence sums mapping), and density functional theory. The material reveals low energy barriers (0.12–0.43 eV) of Li hopping and a possible 3D channel system for Li-ion migration. It is found that only one Li per formula unit can be extracted within the potential stability window of the commercially available electrolytes. The interrelation between dimensionality, topology and energetics of Li-ion diffusion and peculiarities of the Li2CoPO4F crystal structure are discussed in detail.

We have performed broad-band spectroscopic investigations of vibrational and relaxational excitations of water molecules confined to nanocages within artificial beryl and mineral cordierite crystals. Signatures of quantum critical phenomena within the H2O molecular network are registered in beryl. In cordierite, a density functional analysis is applied to reconstruct the potential energy landscape experienced by H2O molecules, revealing a pronounced anisotropy with a potential well of about 10 meV for the molecular dipole moment aligned along the b-axis. This anisotropy leads to a strongly temperature dependent and anisotropic relaxational response of the dipoles at radiofrequencies with the activation energies corresponding to the barriers of the rotational potential. At T ≈ 3 K, we identify signatures of a transition into a glassy state composed by clusters of H2O dipoles. Rich set of anisotropic and temperature-dependent excitations are observed in the terahertz frequency range which we associate with rotational/translational vibrations.

Understanding and controlling the optoelectronic properties of organic semiconductors at the molecular level remains a challenge due to the complexity of chemical structures and intermolecular interactions. A common strategy to address this challenge is to utilize both experimental and computational approaches. In this contribution, we show that density functional theory (DFT) calculation is a useful tool to provide insights into the bonding, electron population distribution, and optical transitions of adducts between conjugated molecules and Lewis acids (CM-LA). Adduct formation leads to relevant modifications of key properties, including a red shift in optical transitions and an increase in charge carrier density and charge mobility, compared to the parent conjugated molecules. We show that electron density transfer from the CM to the LA, which was hypothesized to cause the experimental red shift in absorption spectra upon LA binding, can be quantified and interpreted by population analysis. Experimental red shifts in optical transitions for all molecular families can also be predicted by time-dependent DFT calculations with different density functionals. These detailed insights help to optimize a priori design guidelines for future applications.

Conformational space of polyphenylenevinylene oligomers is systematically investigated computationally at energies relevant for room temperature dynamics in a solvent and in a solid state. Our calculations show that optimal oligomer structures are essentially planar. However, lack of a deep minimum at the planar geometry allows for large molecular deformations even at very low temperatures. At larger angles, rotational motion of dihedrals intermix with two orthogonal bending motions of the entire molecule. In a crystalline environment these degrees of freedom intermix with translational and rotational motions, whereas purely intramolecular modes are well separated. The reliability of our calculations is confirmed by an excellent match of the theoretical and experimental Raman spectra of crystalline stilbene in the entire spectral range including the low-frequency part. Obtained results provide important insights into nature of low-frequency vibrations, which play a key role in charge transport in organic semiconductors.

A series of ten conjugated polymers incorporating in their molecular frameworks extended DADAD building blocks with thiophene donor (D) and either benzotriazole, benzoxadiazole, benzothiadiazole, difluorobenzothiadiazole or quinoxaline acceptor (A) units were synthesized and characterized. The optoelectronic properties of new polymers were computed and experimentally investigated revealing a good relationship, which can guide further rational design of materials with tailored properties for organic photovoltaics using in-silico approaches. The performance of all polymers in organic bulk heterojunction solar cells was compared and some important empirical rules were formulated for reaching the best photovoltaic performance from (X-DADAD)n family of polymers.

A comprehensive DFT study of a set of oligo(p-phenylene vinylene) molecules is performed to understand the structural and electronic changes upon functionalization. These changes are rationalized within a model considering frontier molecular orbitals of the π -conjugated system and σ -bonding orbital by which the functional group is attached to the host molecule. Two simple scalar quantum chemical descriptors are shown to correlate with optoelectronic properties of the functionalized molecule: the electronegativity and the relative electric dipole moment of the smallest π -closed shell subsystem containing the functional group and the terminal segment of the host molecule (phenyl). Both descriptors correlate linearly with the empirical Hammett σ p constant for a set of 24 functional groups. Comparison with available experimental data on UV–vis absorption and cyclic voltammetry is made. Observed structural changes reflect changes in the electronic density.

Reversible electrochemical deintercalation of potassium from the K6(VO)2(V2O3)2(PO4)4(P2O7) phosphate-pyrophosphate-oxide of potassium and vanadium (IV,V) obtained through a ceramic route has been demonstrated. The material has been tested as a high voltage positive electrode (cathode) for K-ion batteries, demonstrating 53% of the theoretical capacity of 88 mAh/g at the current density C/50 in the 1.8–4.4 V vs K/K+ potential range. The crystal structures of K6(VO)2(V2O3)2(PO4)4(P2O7) in the pristine, charged and discharged states were refined by Rietveld method from powder X-ray diffraction data using a structure model with stochastic orientation of the pyrophosphate groups (space group Pnma, a = 6.9891(1)A, b = 13.3735(2)A, c = 14.2495(2)A in the pristine state). In spite of deintercalation of bulky K+ cations, the cell volume change upon charge amounts to 0.9% rendering K6(VO)2(V2O3)2(PO4)4(P2O7) a “low strain” cathode. The potassium (de)intercalation occurs equally from two distinct crystallographic sites through a single ~4.2 V sloped plateau featuring solid-solution-like behavior, which was demonstrated by operando powder X-ray diffraction. The evaluation of diffusion barriers from the first principles has been conducted by the nudged elastic band method for two ordered arrangements of the pyrophosphate groups derived from the refined disordered structure. The diffusion barriers along crystallographic direction b for both investigated ordered variants were found to be below 0.3 eV.

Li-ion superionic conductors play an important role in next-generation energy storage devices. To be applicable, they should meet a wide range of specifications such as safety, efficiency, affordability, and stability. The NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP) compound is a well-known lithium-conductive solid electrolyte, suitable for all-solid-state and redox-flow battery prototypes offers great potential. Yet, despite the high scientific attention paid to LATP, its stability towards environmental exposure to reactive components such as water, carbon dioxide, and oxygen is poorly elucidated. Herein we evaluate under controlled conditions the structure and transport properties of LATP in both air and argon atmosphere to understand the influence of environmental processing effects over a three-month set of experiments. We demonstrate that LATP ceramics (total conductivity σt of 4·10−4 S cm−1 at room temperature; porosity of 18.5 vol %) degrade drastically showing 76% and 28% of the σt losses (for ceramics stored in the air and argon correspondingly). Based on experimental and theoretical approaches, we propose a degradation mechanism supported by Electrochemical Impedance Spectroscopy (EIS), Powder X-Ray Diffraction Analysis (PXRD), Scanning Electron Microscopy (SEM), Energy-Dispersive X-Ray spectroscopy (EDX), and Density Functional Theory (DFT) calculations.

We review recent progress in the modeling of organic solar cells and photovoltaic materials, as well as discuss the underlying theoretical methods with an emphasis on dynamical electronic processes occurring in organic semiconductors. The key feature of the latter is a strong electron-phonon interaction, making the evolution of electronic and structural degrees of freedom inseparable. We discuss commonly used approaches for first-principles modeling of this evolution, focusing on a multiscale framework based on the Holstein–Peierls Hamiltonian solved via polaron transformation. A challenge for both theoretical and experimental investigations of organic solar cells is the complex multiscale morphology of these devices. Nevertheless, predictive modeling of photovoltaic materials and devices is attainable and is rapidly developing, as reviewed here.

A new, pH dependent and water-soluble, conjugated oligomer (amino, trimethylammonium oligophenylene vinylene, ATAOPV) was synthesized with a quaternary ammonium salt and an aromatic amine at the two ends of a π-conjugated oligomer, thus creating a strong dipole across the molecule. A unique white light LED is successfully fabricated from a stimuli responsive organic molecule whose emission properties are dominated by the pH value of the solution through controlled intermolecular charge transfer.

Using quantum mechanical calculations within density functional theory, we provide a comprehensive analysis of infrared-active excitation of water molecules confined in nanocages of a beryl crystal lattice. We calculate infrared-active modes including the translational, librational, and mixed-type resonances of regular and heavy water molecules. The results are compared to the experimental spectra measured for the two principal polarizations of the electric field: parallel and perpendicular to the crystallographic c-axis. Good agreement is achieved between calculated and measured isotopic shifts of the normal modes. We analyze the vibrational modes in connection with the structural characteristics and arrangements of water molecules within the beryl crystal. Specific atomic displacements are assigned to each experimentally detected vibrational mode resolving the properties of nano-confined water on scales not accessible by experiments. Our results elucidate the applicability and efficiency of a combined experimental and computational approach for describing and an in-depth understanding of nano-confined water, and pave the way for future studies of more complex systems.

Four new conjugated polymers based on benzodithiophene, thiophene and 2,1,3-benzothiadiazole or 5,6-difluoro-2,1,3-benzothiadiazole were synthesized and investigated as absorber materials for organic photovoltaics. The effect of (bi)thiophene π-spacers and fluorine substitution on the physicochemical and optoelectronic properties of the polymers was revealed and correlations were drawn with their electrical characteristics in organic solar cells. In particular, introducing either thiophene spacers or fluorine substituents does not affect much the photovoltaic performance of the polymers, while the combination of both routes was found to be a promising strategy for improving the charge carrier mobilities and morphology of the polymer-fullerene blends as well as light power conversion efficiency in solar cells based on these materials. The bulk heterojunction organic solar cells based on the π-bridged and fluorinated polymer P4 showed the highest short-circuit current density and power conversion efficiency of 7 %, which is an inspiring value for fullerene-based organic photovoltaics. Most importantly, our findings provide important insights into rational design of high-performance conjugated polymers while pursuing a combination of two efficient backbone functionalization strategies based on introduction of fluorine substituents and π-spacers to control the geometry and electronic characteristics of the polymer chains.

Using ab initio calculations and classical molecular dynamics simulations coupled to complementary experimental characterization, four molecular semiconductors were investigated in vacuum, solution, and crystalline form. Independently, the molecules can be described as nearly isostructural, yet in crystalline form, two distinct crystal systems are observed with characteristic molecular geometries. The minor structural variations provide a platform to investigate the subtlety of simple substitutions, with particular focus on polymorphism and rotational isomerism. Resolved crystal structures offer an exact description of intermolecular ordering in the solid state. This enables evaluation of molecular binding energy in various crystallographic configurations to fully rationalize observed crystal packing on a basis of first-principle calculations of intermolecular interactions.

A series of PPVO (p-phenylene vinylene oligomer) derivatives with functional groups of varying electronegativity were synthesized via the Horner-Wadsworth-Emmons reaction. Subtle changes in the end group functionality significantly impact the molecular electronic and optical properties of the PPVOs, resulting in broadly tunable and efficient UV absorption and photoluminescence spectra. Of particular interest is the NO2-substituted PPVO which exhibits photoluminescence color ranging from the blue to the red, thus encompassing the entire visible spectrum. Our experimental study and electronic structure calculations suggest that the formation of aggregates and strong dipole-dipole solute-solvent interactions are responsible for the observed strong solvatochromism. Experimental and theoretical results for the NH2-, H-, and NO2-substituted PPVOs suggest that the stabilization of ground or excited state dipoles leads to the blue or red shift of the optical spectra. The electroluminescence (EL) spectra of H-, COOH-, and NO2-PPVO have maxima at 487, 518, and 587 nm, respectively, in the OLED device. This trend in the EL spectra is in excellent agreement with the end group-dependent PL spectra of the PPVO thin-films.

Using ab initio methods we examine the molecular and solid-state electronic properties of a recently synthesized small-molecule donor, p-DTS(PTTh2)2, which belongs to the dithienosilole-pyridylthiadiazole family of chromophores. In combination with the PC70BM acceptor, p-DTS(PTTh2)2 can be used to fabricate high-efficiency bulk heterojunction organic solar cells. A precise picture of molecular structure and interchromophore packing is provided via a single-crystal X-ray diffraction study; such details cannot be easily obtained with donor materials based on conjugated polymers. In first-principles approaches we are limited to a single-crystallite scale. At this scale, according to our investigation, the principal properties responsible for the high efficiency are strong low-energy light absorption by individual molecules, large exciton diffusion length, and fast disorder-resistant hole transport along π-stacks in the crystallite. The calculated exciton diffusion length is substantially larger than the aver...

Single crystal microwires of a well-studied organic semiconductor used in organic solar cells, namely p-DTS(FBTTh2)2, are prepared via a self-assembly method in solution. The high level of intermolecular organization in the single crystals facilitates migration of charges, relative to solution-processed films, and provides insight into the intrinsic charge transport properties of p-DTS(FBTTh2)2. Field-effect transistors based on the microwires can achieve hole mobilities on the order of ≈1.8 cm2 V−1 s−1. Furthermore, these microwires show photoresponsive electrical characteristics and can act as photoswitches, with switch ratios over 1000. These experimental results are interpreted using theoretical simulations using an atomistic density functional theory approach. Based on the lattice organization, intermolecular couplings and reorganization energies are calculated, and hole mobilities for comparison with experimental measurements are further estimated. These results demonstrate a unique example of the optoelectronic applications of p-DTS(FBTTh2)2 microwires.

We argue that semiconducting quenched liquids and frozen glasses may exhibit a set of peculiar electronic states of topological origin. These states reside at strained regions arising during structural reconfigurations between distinct aperiodic states intrinsic to quenched melts. The strained regions are domain walls separating the distinct aperiodic states; their number is about 10(20) cm(-3) in all glassformers owing to the universal dynamics of deeply supercooled melts. Even though located near the middle of the forbidden gap, the topological states are rather extended in one direction while being centered at under- and overcoordinated atoms. The states exhibit the reverse charge-spin relation, the majority of states being diamagnetic and charged. The topological states may be sufficient to account for a number of irradiation-induced phenomena in amorphous semiconductors, including electron spin resonance signal, midgap absorption, photoluminescence, and the fatigue of photoluminescence. We propose experiments to test the present microscopic picture.

We obtain the dynamic correlation function of two-dimensional lattice gas with nearest-neighbor repulsion in ordered c2 2 phase antiferromagnetic ordering under the condition of low concentration of structural defects. It is shown that displacements of defects of the ordered state are responsible for the particle number fluctuations in the probe area. The corresponding set of kinetic equations is derived and solved in linear approximation on the defect concentration. Three types of strongly correlated complex jumps are considered and their contribution to fluctuations is analyzed. These are jumps of excess particles, vacancies and flip-flop jumps. The kinetic approach is more general than the one based on diffusionlike equations used in our previous papers. Thus, it becomes possible to adequately describe correlations of fluctuations at small times, where our previous theory fails to give correct results. Our analytical results for fluctuations of particle number in the probe area agree well with those obtained by Monte Carlo simulations.

Semiconductor glasses exhibit many unique optical and electronic anomalies. We have put forth a semi-phenomenological scenario (J. Chem. Phys. 132, 044508 (2010)) in which several of these anomalies arise from deep midgap electronic states residing on high-strain regions intrinsic to the activated transport above the glass transition. Here we demonstrate at the molecular level how this scenario is realized in an important class of semiconductor glasses, namely chalcogen and pnictogen containing alloys. Both the glass itself and the intrinsic electronic midgap states emerge as a result of the formation of a network composed of $\sigma$-bonded atomic $p$-orbitals that are only weakly hybridized. Despite a large number of weak bonds, these $pp\sigma$-networks are stable with respect to competing types of bonding, while exhibiting a high degree of structural degeneracy. The stability is rationalized with the help of a hereby proposed structural model, by which $pp\sigma$-networks are symmetry-broken and distorted versions of a high symmetry structure. The latter structure exhibits exact octahedral coordination and is fully covalently-bonded. The present approach provides a microscopic route to a fully consistent description of the electronic and structural excitations in vitreous semiconductors., Comment: 22 pages, 17 figures, revised version, final version to appear in J. Chem. Phys

A new effect of 'two-stroke charge pump' has been experimentally observed in nano-Si, which is based on the Auger process ejecting charge carriers from a silicon nanocrystalline core into enveloping SiOx layer. The effect is important for understanding the nature of such phenomena as dimensional decrease of quantum efficiency of emission, space separation of charge carriers and peculiarities of their localisation. A new mechanism of charge carrier localisation by 'topological' traps in undulating quantum wires has been considered. The developed models are supported by the results of comprehensive spectral investigations of photoluminescence, thermoluminescence, and tunnelling luminescence.