171 research outputs found
Interaction energies of monosubstituted benzene dimers via nonlocal density functional theory
We present density-functional calculations for the interaction energy of
monosubstituted benzene dimers. Our approach utilizes a recently developed
fully nonlocal correlation energy functional, which has been applied to the
pure benzene dimer and several other systems with promising results. The
interaction energy as a function of monomer distance was calculated for four
different substituents in a sandwich and two T-shaped configurations. In
addition, we considered two methods for dealing with exchange, namely using the
revPBE generalized gradient functional as well as full Hartree-Fock. Our
results are compared with other methods, such as Moller-Plesset and
coupled-cluster calculations, thereby establishing the usefulness of our
approach. Since our density-functional based method is considerably faster than
other standard methods, it provides a computational inexpensive alternative,
which is of particular interest for larger systems where standard calculations
are too expensive or infeasible.Comment: submitted to J. Chem. Phy
Tight-Binding model for semiconductor nanostructures
An empirical tight-binding (TB) model is applied to the
investigation of electronic states in semiconductor quantum dots. A basis set
of three -orbitals at the anions and one -orbital at the cations is
chosen. Matrix elements up to the second nearest neighbors and the spin-orbit
coupling are included in our TB-model. The parametrization is chosen so that
the effective masses, the spin-orbit-splitting and the gap energy of the bulk
CdSe and ZnSe are reproduced. Within this reduced TB-basis the
valence (p-) bands are excellently reproduced and the conduction (s-) band is
well reproduced close to the -point, i.e. near to the band gap. In
terms of this model much larger systems can be described than within a (more
realistic) -basis. The quantum dot is modelled by using the (bulk)
TB-parameters for the particular material at those sites occupied by atoms of
this material. Within this TB-model we study pyramidal-shaped CdSe quantum dots
embedded in a ZnSe matrix and free spherical CdSe quantum dots (nanocrystals).
Strain-effects are included by using an appropriate model strain field. Within
the TB-model, the strain-effects can be artifically switched off to investigate
the infuence of strain on the bound electronic states and, in particular, their
spatial orientation. The theoretical results for spherical nanocrystals are
compared with data from tunneling spectroscopy and optical experiments.
Furthermore the influence of the spin-orbit coupling is investigated
Ab initio van der Waals interactions in simulations of water alter structure from mainly tetrahedral to high-density-like
The structure of liquid water at ambient conditions is studied in ab initio
molecular dynamics simulations using van der Waals (vdW) density-functional
theory, i.e. using the new exchange-correlation functionals optPBE-vdW and
vdW-DF2. Inclusion of the more isotropic vdW interactions counteracts highly
directional hydrogen-bonds, which are enhanced by standard functionals. This
brings about a softening of the microscopic structure of water, as seen from
the broadening of angular distribution functions and, in particular, from the
much lower and broader first peak in the oxygen-oxygen pair-correlation
function (PCF), indicating loss of structure in the outer solvation shells. In
combination with softer non-local correlation terms, as in the new
parameterization of vdW-DF, inclusion of vdW interactions is shown to shift the
balance of resulting structures from open tetrahedral to more close-packed. The
resulting O-O PCF shows some resemblance with experiment for high-density water
(A. K. Soper and M. A. Ricci, Phys. Rev. Lett., 84:2881, 2000), but not
directly with experiment for ambient water. However, an O-O PCF consisting of a
linear combination of 70% from vdW-DF2 and 30% from experiment on low-density
liquid water reproduces near-quantitatively the experimental O-O PCF for
ambient water, indicating consistency with a two-liquid model with fluctuations
between high- and low-density regions
Phonon Raman spectra of colloidal CdTe nanocrystals: effect of size, non-stoichiometry and ligand exchange
Resonant Raman study reveals the noticeable effect of the ligand exchange on the nanocrystal (NC) surface onto the phonon spectra of colloidal CdTe NC of different size and composition. The oleic acid ligand exchange for pyridine ones was found to change noticeably the position and width of the longitudinal optical (LO) phonon mode, as well as its intensity ratio to overtones. The broad shoulder above the LO peak frequency was enhanced and sharpened after pyridine treatment, as well as with decreasing NC size. The low-frequency mode around 100 cm-1 which is commonly related with the disorder-activated acoustical phonons appears in smaller NCs but is not enhanced after pyridine treatment. Surprisingly, the feature at low-frequency shoulder of the LO peak, commonly assigned to the surface optical phonon mode, was not sensitive to ligand exchange and concomitant close packing of the NCs. An increased structural disorder on the NC surface, strain and modified electron-phonon coupling is discussed as the possible reason of the observed changes in the phonon spectrum of ligand-exchanged CdTe NCs
Lateral electrical transport, optical properties and photocurrent measurements in two-dimensional arrays of silicon nanocrystals embedded in SiO2
In this study we investigate the electronic transport, the optical properties, and photocurrent in two-dimensional arrays of silicon nanocrystals (Si NCs) embedded in silicon dioxide, grown on quartz and having sizes in the range between less than 2 and 20 nm. Electronic transport is determined by the collective effect of Coulomb blockade gaps in the Si NCs. Absorption spectra show the well-known upshift of the energy bandgap with decreasing NC size. Photocurrent follows the absorption spectra confirming that it is composed of photo-generated carriers within the Si NCs. In films containing Si NCs with sizes less than 2 nm, strong quantum confinement and exciton localization are observed, resulting in light emission and absence of photocurrent. Our results show that Si NCs are useful building blocks of photovoltaic devices for use as better absorbers than bulk Si in the visible and ultraviolet spectral range. However, when strong quantum confinement effects come into play, carrier transport is significantly reduced due to strong exciton localization and Coulomb blockade effects, thus leading to limited photocurrent
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