33 research outputs found
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Charge delocalization characteristics of regioregular high mobility polymers.
Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. This work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part II: The intrinsic electronic midgap states
We propose a structural model that treats in a unified fashion both the
atomic motions and electronic excitations in quenched melts of pnictide and
chalcogenide semiconductors. In Part I (submitted to J. Chem. Phys.), we argued
these quenched melts represent aperiodic -networks that are highly
stable and, at the same time, structurally degenerate. These networks are
characterized by a continuous range of coordination. Here we present a
systematic way to classify these types of coordination in terms of discrete
coordination defects in a parent structure defined on a simple cubic lattice.
We identify the lowest energy coordination defects with the intrinsic midgap
electronic states in semiconductor glasses, which were argued earlier to cause
many of the unique optoelectronic anomalies in these materials. In addition,
these coordination defects are mobile and correspond to the transition state
configurations during the activated transport above the glass transition. The
presence of the coordination defects may account for the puzzling discrepancy
between the kinetic and thermodynamic fragility in chalcogenides. Finally, the
proposed model recovers as limiting cases several popular types of bonding
patterns proposed earlier, including: valence-alternation pairs, hypervalent
configurations, and homopolar bonds in heteropolar compounds.Comment: 17 pages, 15 figures, revised version, final version to appear in J.
Chem. Phy
Electronic structure and the glass transition in pnictide and chalcogenide semiconductor alloys. Part I: The formation of the -network
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 -bonded atomic -orbitals that are only weakly
hybridized. Despite a large number of weak bonds, these -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 -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. Phy
Dynamic correlations in an ordered c(22) lattice gas
We obtain the dynamic correlation function of two-dimensional lattice gas
with nearest-neighbor repulsion in ordered c(22) 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
analysed. These are jumps of excess particles, vacancies and flip-flop jumps.
The kinetic approach is more general than the one based on diffusion-like
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 new analytical results for fluctuations of
particle number in the probe area agree well with those obtained by Monte Carlo
simulations.Comment: 10 pages, 7 figure
Recommended from our members
Charge delocalization characteristics of regioregular high mobility polymers.
Controlling the regioregularity among the structural units of narrow bandgap conjugated polymer backbones has led to improvements in optoelectronic properties, for example in the mobilities observed in field effect transistor devices. To investigate how the regioregularity affects quantities relevant to hole transport, regioregular and regiorandom oligomers representative of polymeric structures were studied using density functional theory. Several structural and electronic characteristics of the oligomers were compared, including chain planarity, cation spin density, excess charges on molecular units and internal reorganizational energy. The main difference between the regioregular and regiorandom oligomers is found to be the conjugated backbone planarity, while the reorganizational energies calculated are quite similar across the molecular family. This work constitutes the first step on understanding the complex interplay of atomistic changes and an oligomer backbone structure toward modeling the charge transport properties
Crystal Structure and Li-Ion Transport in Li<sub>2</sub>CoPO<sub>4</sub>F High-Voltage Cathode Material for Li-Ion Batteries
In
this work, we provide a structural and computational investigation
of the Li<sub>2</sub>CoPO<sub>4</sub>F high-voltage cathode material
by means of neutron powder diffraction (SG <i>Pnma</i>, <i>a</i> = 10.4528(2) Ã…, <i>b</i> = 6.38667(10)
Å, <i>c</i> = 10.8764(2) Å, <i>R</i><sub>F</sub> = 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 Li<sub>2</sub>CoPO<sub>4</sub>F crystal structure are discussed in detail