Nonmonotonic Size-Dependent Carrier Mobility in PbSe Nanocrystal Arrays

On the basis of a tight binding system-bath model, we investigated carrier mobility of PbSe nanocrystal (NC) arrays as a function of NC size and inter-NC separation. The size-dependent trend of calculated carrier mobilities are in excellent agreement with recent experimental measurements: electron mobility increased up to NC diameter of ∼6 nm and then decreased for larger NCs, whereas hole mobility showed a monotonic size-dependency. Carrier mobility increase was associated with reduced activation energy that governs charge-transfer processes. In contrast, the decrease in electron mobility for large NCs was found to be due to smaller electronic coupling. Control of inter-NC separation is crucial for mobility enhancement: the mobility may change by an order of magnitude when inter-NC separation varies by as little as 1 to 2 Å. We anticipate similar size-dependency of the mobility in other semiconductor NC arrays, although crossover diameter in which mobility reaches its maximum depends on the material

Improved DFT Potential Energy Surfaces via Improved Densities

Density-corrected DFT is a method that cures several failures of self-consistent semilocal DFT calculations by using a more accurate density instead. A novel procedure employs the Hartree–Fock density to bonds that are more severely stretched than ever before. This substantially increases the range of accurate potential energy surfaces obtainable from semilocal DFT for many heteronuclear molecules. We show that this works for both neutral and charged molecules. We explain why and explore more difficult cases, for example, CH⁺, where density-corrected DFT results are even better than sophisticated methods like CCSD. We give a simple criterion for when DC-DFT should be more accurate than self-consistent DFT that can be applied for most cases

Benchmarks and Reliable DFT Results for Spin Gaps of Small Ligand Fe(II) Complexes

All-electron fixed-node diffusion Monte Carlo provides benchmark spin gaps for four Fe­(II) octahedral complexes. Standard quantum chemical methods (semilocal DFT and CCSD­(T)) fail badly for the energy difference between their high- and low-spin states. Density-corrected DFT is both significantly more accurate and reliable and yields a consistent prediction for the Fe–Porphyrin complex

Identification of Droplet-Flow-Induced Electric Energy on Electrolyte–Insulator–Semiconductor Structure

Recently, various energy transducers driven by the relative motion of solids and liquids have been demonstrated. However, in relation to the energy transducer, a proper understanding of the dynamic behavior of ions remains unclear. Moreover, the energy density is low for practical usage mainly due to structural limitations, a lack of material development stemming from the currently poor understanding of the mechanisms, and the intermittently generated electricity given the characteristics of the water motion (pulsed signals). Here, we verify a hypothesis pertaining to the ion dynamics which govern the operation mechanism of the transducer. In addition, we demonstrate enhanced energy transducer to convert the mechanical energy of flowing water droplets into continuous electrical energy using an electrolyte–insulator–semiconductor structure as a device structure. The output power per droplet mass and the ratio of generated electric energy to the kinetic energy of water drops are 0.149<i>v</i>² mW·g^–1·m^–2·s² and 29.8%, respectively, where <i>v</i> is the speed of the water droplet

High-Voltage Symmetric Nonaqueous Redox Flow Battery Based on Modularly Tunable [Ru₂M(μ₃‑O)(CH₃CO₂)₆(py)₃] (M = Ru, Mn, Co, Ni, Zn) Cluster Compounds with Multielectron Storage Capability

Redox flow batteries (RFBs) provide an attractive solution for large-scale energy buffering and storage. This report describes the development of nonaqueous RFBs based on trimetallic coordination cluster compounds: [Ru2M(μ3-O)(CH3CO2)6(py)3] (M = Ru, Mn, Co, Ni, Zn). The all-ruthenium complex exhibited stable battery cycles in anolyte–catholyte symmetric operation, with rarely observed multielectron storage in a single molecule. Moreover, the complex holds modularly tunable synthetic handles for systematic improvements in solubility and redox potentials. An optimized battery stack containing [Ru3(μ3-O)(CH3CO2)6(py)3]+ anolyte and [Ru2Co(μ3-O)(CH3CO2)6(py)3] catholyte yielded stable cycles with a discharge voltage of 2.4 V, comparable to the state-of-the-art nonaqueous RFBs. Explanation for the exceptional stability of the charged states and prediction of systematic tunability of the redox potentials of the cluster compounds were assisted by DFT calculations

Investigation and Control of Single Molecular Structures of <i>Meso</i>–<i>Meso</i> Linked Long Porphyrin Arrays

We have investigated conformational structures of <i>meso</i>–<i>meso</i> linked porphyrin arrays (<b>Z<i>n</i></b>) by single molecule fluorescence spectroscopy. Modulation depths (<i>M</i> values) were measured by excitation polarization fluorescence spectroscopy. The <i>M</i> value decreases from 0.85 to 0.46 as the number of porphyrin units increases from 3 to 128, indicating that longer arrays exhibit coiled structures. Such conformational changes depending on the length have been confirmed by coarse-grained simulation. The histograms of <i>M</i> values and traces of centroid position of emitting sites by localization microscopy showed that the structures of longer arrays changed to more stretched after solvent vapor annealing with tetrahydrofuran

Conversion between Metavalent and Covalent Bond in Metastable Superlattices Composed of 2D and 3D Sublayers

Reversible conversion over multimillion times in bond types between metavalent and covalent bonds becomes one of the most promising bases for universal memory. As the conversions have been found in metastable states, an extended category of crystal structures from stable states via redistribution of vacancies, research on kinetic behavior of the vacancies is highly in demand. However, it remains lacking due to difficulties with experimental analysis. Herein, the direct observation of the evolution of chemical states of vacancies clarifies the behavior by combining analysis on charge density distribution, electrical conductivity, and crystal structures. Site-switching of vacancies of Sb2Te3 gradually occurs with diverged energy barriers owing to their own activation code: the accumulation of vacancies triggers spontaneous gliding along atomic planes to relieve electrostatic repulsion. Studies on the behavior can be further applied to multiphase superlattices composed of Sb2Te3 (2D) and GeTe (3D) sublayers, which represent superior memory performances, but their operating mechanisms were still under debate due to their complexity. The site-switching is favorable (suppressed) when Te–Te bonds are formed as physisorption (chemisorption) over the interface between Sb2Te3 (2D) and GeTe (3D) sublayers driven by configurational entropic gain (electrostatic enthalpic loss). Depending on the type of interfaces between sublayers, phases of the superlattices are classified into metastable and stable states, where the conversion could only be achieved in the metastable state. From this comprehensive understanding on the operating mechanism via kinetic behaviors of vacancies and the metastability, further studies toward vacancy engineering are expected in versatile materials

The Role of Linkers in the Excited-State Dynamic Planarization Processes of Macrocyclic Oligothiophene 12-Mers

Linkers adjoining chromophores play an important role in modulating the structure of conjugated systems, which is bound up with their photophysical properties. However, to date, the focus of works dealing with linker effects was limited only to linear π-conjugated materials, and there have been no detailed studies on cyclic counterparts. Herein we report the linker effects on the dynamic planarization processes of π-conjugated macrocyclic oligothiophene 12-mers, where the different ratio between ethynylene and vinylene linkers was chosen to control the backbone rigidity. By analyzing transient fluorescence spectra, we demonstrate that the connecting linkers play a crucial role in the excited-state dynamics of cyclic conjugated systems. Faster dynamic planarization, longer exciton delocalization length, and higher degree of planarity were observed in vinylene inserted cyclic oligothiophenes. Molecular dynamics simulations and density functional theory calculations also stress the importance of the role of linkers in modulating the structure of cyclic oligothiophenes