81 research outputs found
Energy Gap from Step Structure of the Analytically Inverted Non-Additive Kinetic Potential
The bandgap constitutes a challenging problem in density functional theory
(DFT) methodologies. It is known that the energy gap values calculated by
common DFT approaches are underestimated. The bandgap was also found to be
related to the derivative discontinuity (DD) of the exchange-correlation
potential in the Kohn-Sham formulation of DFT. Several reports have shown that
DD appears as a step on the potential curve. The step structure is a mandatory
structure for aligning the KS energy levels in the ionization potentials in a
dissociated molecule in both fragments and is a function of electron
localisation. Reproducing the step in the DFT framework gives the charge
transfer process and the correct energy gap and describes the source of
dissociation. This step phenomenon has not yet been studied in the non-additive
kinetic potential , a key quantity
used in embedding theories. While
is known to be difficult to approximate, in this work, we explain how an
accurate energy gap can be produced from the analytically inverted
, even if we use the input densities
calculated by the local and semi-local functionals. We used the precisely
calculated reported in our previous
publication [Phys. Rev. A 106, 042812 (2022)] to produce the energy gap for
some model systems and report in this work the promising accuracy of our
results through the comparison with the results obtained from one of the most
accurate calculations, OEP theory with the KLI local approximation.Comment: 33 pages, 18 figure
Atomistic Mechanisms of Sliding in Few-Layer and Bulk Doped MoS
Sliding of two-dimensional materials is critical for their application as
solid lubricants for space, and also relevant for strain engineering and device
fabrication. Dopants such as Ni surprisingly improve lubrication in MoS,
despite formation of interlayer bonds by intercalated Ni, and the mechanism has
remained unclear. While sliding on the atomistic level has been theoretically
investigated in pristine 2D materials, there has been little work on doped
forms, especially for the complicated case of intercalation. We use density
functional theory to study sliding of Ni-doped MoS, considering Mo/S
substitution and octahedral/tetrahedral intercalation. We find that bulk and
trilayers are well described by pairwise bilayer interactions. Tetrahedral
intercalation between layers dramatically increases their sliding barrier, but
minimally affects sliding between adjacent undoped layers, thus preserving
effective lubrication. We provide an atomistic view of how sliding occurs in
doped transition-metal dichalcogenides, and a general methodology to analyze
doped sliding.Comment: 19 pages, 5 figure
Computational generation of voids in -Si and -Si:H by cavitation at low density
Use of amorphous silicon (-Si) and hydrogenated amorphous silicon
(-Si:H) in photovoltaics has been limited by light-induced degradation (the
Staebler-Wronski effect) and low hole mobilities, and voids have been
implicated in both problems. Accurately modeling the void microstructure is
critical to theoretically understanding the cause of these issues. Previous
methods of modeling voids have involved removing atoms according to an {\it a
priori} idea of void structure and/or using computationally expensive molecular
dynamics. We propose a new fast and unbiased approach based on the established
and efficient Wooten-Winer-Weaire (WWW) Monte Carlo method, by using a range of
fixed densities to generate equilibrium structures of -Si and -Si:H that
maintain 4-coordination. We find a smooth evolution in bond lengths, bond
angles, and bond angle deviations as the density is changed
around the equilibrium value of atoms/cm. However, a
significant change occurs at densities below atoms/cm,
where voids begin to form to relieve tensile stress, akin to a cavitation
process in liquids. We find both small voids (radius 3 \AA) and larger
ones (up to 7 \AA), which compare well with available experimental data. The
voids have an influence on atomic structure up to 4 \AA beyond the void surface
and are associated with decreasing structural order, measured by
. We also observe an increasing medium-range dihedral order with
increasing density. Our method allows fast generation of statistical ensembles,
resembles a physical process during experimental deposition, and provides a set
of void structures for further studies of their effects on degradation, hole
mobility, two-level systems, thermal transport, and elastic properties.Comment: 23 pages, 8 figure
Stress effects on vibrational spectra of a cubic hybrid perovskite: A probe of local strain
Inhomogeneous strain may develop in hybrid organic metal-halide perovskite
thin films due to thermal expansion mismatch with a fabrication substrate,
polycrystallinity or even light soaking. Measuring these spatially varying
strains is difficult but of prime importance for understanding the effects on
carrier mobility, non-radiative recombination, degradation and other
optoelectronic properties. Local strain can be mapped using the shifts in
vibrational frequencies using Raman or infrared microscopy. We use density
functional theory to investigate the effect of uniaxial strain on the
vibrations of pseudo-cubic methylammonium lead iodide (CHNHPbI),
and identify the vibrational modes most favorable for local strain mapping (86
cm, 97 cm, 1457 cm, and 1537 cm) and provide
calibration curves. We explain the origin of the frequency changes with strain
using dynamical matrix and mode eigenvector analysis and study strain-induced
structural changes. We also calculate mode Gr\"uneisen parameters, giving
information about anharmonicity and anisotropic negative thermal expansion as
recently reported for other phases. Our results provide a basis for strain
mapping in hybrid perovskites to further the understanding and control of
strain, and improve stability and photovoltaic performance.Comment: 41 pages, 10 figure
Thermodynamic limits to energy conversion in solar thermal fuels
Solar thermal fuels (STFs) are an unconventional paradigm for solar energy
conversion and storage which is attracting renewed attention. In this concept,
a material absorbs sunlight and stores the energy chemically via an induced
structural change, which can later be reversed to release the energy as heat.
An example is the azobenzene molecule which has a cis-trans photoisomerization
with these properties, and can be tuned by chemical substitution and attachment
to templates such as carbon nanotubes, small molecules, or polymers. By analogy
to the Shockley-Queisser limit for photovoltaics, we analyze the maximum
attainable efficiency for STFs from fundamental thermodynamic considerations.
Microscopic reversibility provides a bound on the quantum yield of
photoisomerization due to fluorescence, regardless of details of
photochemistry. We emphasize the importance of analyzing the free energy, not
just enthalpy, of the metastable molecules, and find an efficiency limit for
conversion to stored chemical energy equal to the Shockley-Queisser limit. STF
candidates from a recent high-throughput search are analyzed in light of the
efficiency limit.Comment: 16 pages, 4 figure
Stress effects on the Raman spectrum of an amorphous material: theory and experiment on a-Si:H
Strain in a material induces shifts in vibrational frequencies, which is a
probe of the nature of the vibrations and interatomic potentials, and can be
used to map local stress/strain distributions via Raman microscopy. This method
is standard for crystalline silicon devices, but due to lack of calibration
relations, it has not been applied to amorphous materials such as hydrogenated
amorphous silicon (a-Si:H), a widely studied material for thin-film
photovoltaic and electronic devices. We calculated the Raman spectrum of a-Si:H
\ab initio under different strains and found peak shifts . This
proportionality to the trace of the strain is the general form for isotropic
amorphous vibrational modes, as we show by symmetry analysis and explicit
computation. We also performed Raman measurements under strain and found a
consistent coefficient of . These results
demonstrate that a reliable calibration for the Raman/strain relation can be
achieved even for the broad peaks of an amorphous material, with similar
accuracy and precision as for crystalline materials.Comment: 12 pages, 3 figures + supplementary 8 pages, 4 figure
Basis set effects on the hyperpolarizability of CHCl_3: Gaussian-type orbitals, numerical basis sets and real-space grids
Calculations of the hyperpolarizability are typically much more difficult to
converge with basis set size than the linear polarizability. In order to
understand these convergence issues and hence obtain accurate ab initio values,
we compare calculations of the static hyperpolarizability of the gas-phase
chloroform molecule (CHCl_3) using three different kinds of basis sets:
Gaussian-type orbitals, numerical basis sets, and real-space grids. Although
all of these methods can yield similar results, surprisingly large, diffuse
basis sets are needed to achieve convergence to comparable values. These
results are interpreted in terms of local polarizability and
hyperpolarizability densities. We find that the hyperpolarizability is very
sensitive to the molecular structure, and we also assess the significance of
vibrational contributions and frequency dispersion
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