Deconvoluting Energy Transport Mechanisms in Metal Halide Perovskites Using CsPbBr3 Nanowires as a Model System

Understanding energy transport in metal halide perovskites is essential to effectively guide further optimization of materials and device designs. However, difficulties to disentangle charge carrier diffusion, photon recycling, and photon transport have led to contradicting reports and uncertainty regarding which mechanism dominates. In this study, monocrystalline CsPbBr₃ nanowires serve as 1D model systems to help unravel the respective contribution of energy transport processes in metal-halide perovskites. Spatially, temporally, and spectrally resolved photoluminescence (PL) microscopy reveals characteristic signatures of each transport mechanism from which a robust model describing the PL signal accounting for carrier diffusion, photon propagation, and photon recycling is developed. For the investigated CsPbBr₃ nanowires, an ambipolar carrier mobility of μ = 35 cm² V⁻¹ s⁻¹ is determined, and is found that charge carrier diffusion dominates the energy transport process over photon recycling. Moreover, the general applicability of the developed model is demonstrated on different perovskite compounds by applying it to data provided in previous related reports, from which clarity is gained as to why conflicting reports exist. These findings, therefore, serve as a useful tool to assist future studies aimed at characterizing energy transport mechanisms in semiconductor nanowires using PL.     

Doping‐Induced Absorption Bands in P3HT: Polarons and Bipolarons

In this work, we focus on the formation of different kinds of charge carriers such as polarons and bipolarons upon p‐type doping (oxidation) of the organic semiconductor poly(3‐ hexylthiophene‐2,5‐diyl) (P3HT). We elucidate the cyclic voltammogram during oxidation of this polymer and present spectroscopic changes upon doping in the UV/Vis/near‐IR range as well as in the mid‐IR range. In the low‐oxidation regime, two absorption bands related to sub‐gap transitions appear, one in the UV/Vis range and another one in the mid‐IR range. The UV/Vis absorption gradually decreases upon further doping while the mid‐IR absorption shifts to lower energy. Additionally, electron paramagnetic resonance (EPR) measurements are performed, showing an increase of the EPR signal up to a certain doping level, which significantly decreases upon further doping. Furthermore, the absorption spectra in the UV/Vis range are analyzed in relation to the morphology (crystalline vs. amorphous) by using theoretical models. Finally, the calculated charge carriers from cyclic voltammogram are linked together with optical transitions as well as with the EPR signals upon p‐type doping. We stress that our results indicate the formation of polarons at low doping levels and the existence of bipolarons at high doping levels. The presented spectroscopic data are an experimental evidence of the formation of bipolarons in P3HT.     

Vibrational energy relaxation rates of H2 and D2 in liquid argon via the linearized semiclassical method

The vibrational energy relaxation (VER) rates for H2 and D2 in liquid argon (T=152 K, rho=1.45x1022 cm-3) are calculated using the linearized semiclassical (LSC) method (J. Phys. Chem. 2003, 107, 9059, 9070). The calculation is based on Fermi's golden rule. The VER rate constant is expressed in terms of the quantum-mechanical force-force correlation function, which is then estimated using the LSC method. A local harmonic approximation (LHA) is employed in order to compute the multidimensional Wigner integrals underlying the LSC approximation. The H2-Ar and D2-Ar interactions are described by the three-body potential of Bissonette et al. (J. Phys. Chem. A 1996, 105, 2639). The LHA-LSC-based VER rate constants for both D2 and H2 are found to be about 2-3 orders of magnitude slower than those obtained experimentally. However, their ratio agrees quantitatively with the corresponding experimental result. In contrast, the classical VER rate constants are found to be 8-9 orders of magnitude slower than those obtained experimentally, and their ratio is found to be qualitatively different from the corresponding experimental result.     

Flocking With Short-Range Interactions

Journal of Statistical Physics - We study the large-time behavior of continuum alignment dynamics based on Cucker–Smale (CS)-type interactions which involve short-range kernels, that is,...     

$$(O( V \oplus F), O( V))$$ is a Gelfand pair for any quadratic space V over a local field F

Let V be a quadratic space with a form q over an arbitrary local field F of characteristic different from 2. Let with the form Q extending q with Q(e) = 1. Consider the standard embedding and the two-sided action of on . In this note we show that any -invariant distribution on is invariant with respect to transposition. This result was earlier proven in a bit different form in van Dijk (Math Z 193:581–593, 1986) for , in Aparicio and van Dijk (Complex generalized Gelfand pairs. Tambov University, 2006) for and in Bosman and van Dijk (Geometriae Dedicata 50:261–282, 1994) for p-adic fields. Here we give a different proof. Using results from Aizenbud et al. (arXiv:0709.1273 (math.RT), submitted), we show that this result on invariant distributions implies that the pair (O(V), O(W)) is a Gelfand pair. In the archimedean setting this means that for any irreducible admissible smooth Fréchet representation (π, E) of we have A stronger result for p-adic fields is obtained in Aizenbud et al. (arXiv:0709.4215 (math.RT), submitted).     

Stability of an encapsulated bubble shell

The stability of an encapsulated bubble filled with gas is studied where gas is allowed to diffuse out of the bubble. A mechanistic model that takes into account shell stiffness and surface tension is considered. A critical shell radius for loss of mechanical stability is derived based on a technique adapted for small radius, where surface tension effects become substantial. A new parameter is defined that determines the relative importance of surface tension forces and shell stiffness for shell stability. The developed technique allows to predict, for a given bubble population and gas saturation level of the surrounding liquid, a range of bubble sizes which may collapse in time. Surface tension effects are dominant in determining the critical radius but have a negligible effect on the minimal radius for collapse. The influence of the surface tension on the stability of the shell is illustrated for Optison, a typical ultrasound contrast agent.     

Improving the transport performance in delay tolerant networks by random linear network coding and global acknowledgments

We propose and study a new set of enhancement features to improve the performance of reliable transport in Delay Tolerant Networks (DTNs) consisting of both unicast and multicast flows. The improvement in reliability is brought in by a novel Global Selective ACKnowledgment (G-SACK) scheme and random linear network coding. The motivation for using network coding and G-SACKs comes from the observation that one should take the maximum advantage of the contact opportunities which occur quite infrequently in DTNs. Network coding and G-SACKs perform “mixing” of packet and acknowledgment information, respectively, at the contact opportunities and essentially solve the randomness and finite capacity limitations of DTNs. In contrast to earlier work on network coding in DTNs, we observe and explain the gains due to network coding even under an inter-session setting. Our results from extensive simulations of appropriately chosen “minimal” topologies quantify the gains due to each enhancement feature. We show that substantial gains can be achieved by our proposed enhancements that are very simple to implement.     

Gate‐Induced Modification of Water Adsorption on Dielectrics Probed by EFM and Carbon Nanotube FETs

Humidity plays an important role in molecular electronics. It facilitates charge movement on top of dielectric layers and modifies the device transfer characteristics. Using two different methods to probe temporal charge redistribution on the surface of dielectrics, we were able to extract the surface humidity for the first time. The first method is based on the relaxation time constants of the current through carbon nanotube field‐effect transistors (CNTFETs), and the second is based on electric force microscopy (EFM) measurements. Moreover, we found that applying external gate biases modifies the surface humidity. A theoretical model based on dielectrophoretic attraction between the water molecules and the substrate is introduced to explain this observation, and the results support our hypothesis. Furthermore, it is found that upon the adsorption of two to three layers of water the surface conductivity saturates.     

Nash equilibrium based fairness

There are several approaches of sharing resources among users. There is a noncooperative approach wherein each user strives to maximize its own utility. The most common optimality notion is then the Nash equilibrium. Nash equilibria are generally Pareto inefficient. On the other hand, we consider a Nash equilibrium to be fair as it is defined in a context of fair competition without coalitions (such as cartels and syndicates). We show a general framework of systems wherein there exists a Pareto optimal allocation that is Pareto superior to an inefficient Nash equilibrium. We consider this Pareto optimum to be ??Nash equilibrium based fair.?? We further define a ??Nash proportionately fair?? Pareto optimum. We then provide conditions for the existence of a Pareto-optimal allocation that is, truly or most closely, proportional to a Nash equilibrium. As examples that fit in the above framework, we consider noncooperative flow-control problems in communication networks, for which we show the conditions on the existence of Nash-proportionately fair Pareto optimal allocations.