591 research outputs found
Analytic Energy Gradients for Multiconfigurational Self-Consistent Field Second-Order Quasidegenerate Perturbation Theory (MC-QDPT)
An analytic energy gradient method for second-order quasidegenerate perturbation theory with multiconfigurational self-consistent field reference functions (MC-QDPT) is derived along the lines of the response function formalism (RFF). According to the RFF, the gradients are calculated without solving coupled perturbed equations. Instead, it is necessary to solve seven sets of linear equations in order to determine Lagrangian multipliers, corresponding to four sets of parameter constraining conditions and three sets of additional parameter defining conditions in the Lagrangian. Just one of these linear equations is a large scale linear equation; the others are reducible to just partial differentiations or simple equations solvable by straightforward subroutines
A Doubly Nudged Elastic Band Method for Finding Transition States
A modification of the nudged elastic band (NEB) method is presented that
enables stable optimisations to be run using both the limited-memory
quasi-Newton (L-BFGS) and slow-response quenched velocity Verlet (SQVV)
minimisers. The performance of this new `doubly nudged' DNEB method is analysed
in conjunction with both minimisers and compared with previous NEB
formulations. We find that the fastest DNEB approach (DNEB/L-BFGS) can be
quicker by up to two orders of magnitude. Applications to permutational
rearrangements of the seven-atom Lennard-Jones cluster (LJ7) and highly
cooperative rearrangements of LJ38 and LJ75 are presented. We also outline an
updated algorithm for constructing complicated multi-step pathways using
successive DNEB runs.Comment: 13 pages, 8 figures, 2 table
Investigation of A1g phonons in YBa2Cu3O7 by means of LAPW atomic-force calculations
We report first-principles frozen-phonon calculations for the determination
of the force-free geometry and the dynamical matrix of the five Raman-active
A1g modes in YBa2Cu3O7. To establish the shape of the phonon potentials atomic
forces are calculated within the LAPW method. Two different schemes - the local
density approximation (LDA) and a generalized gradient approximation (GGA) -
are employed for the treatment of electronic exchange and correlation effects.
We find that in the case of LDA the resulting phonon frequencies show a
deviation from experimental values of approximately -10%. Invoking GGA the
frequency values are significantly improved and also the eigenvectors are in
very good agreement with experimental findings.Comment: 15 page
Structure-Sensitive Mechanism of Nanographene Failure
The response of a nanographene sheet to external stresses is considered in
terms of a mechanochemical reaction. The quantum chemical realization of the
approach is based on a coordinate-of-reaction concept for the purpose of
introducing a mechanochemical internal coordinate (MIC) that specifies a
deformational mode. The related force of response is calculated as the energy
gradient along the MIC, while the atomic configuration is optimized over all of
the other coordinates under the MIC constant-pitch elongation. The approach is
applied to the benzene molecule and (5, 5) nanographene. A drastic anisotropy
in the microscopic behavior of both objects under elongation along a MIC has
been observed when the MIC is oriented either along or normally to the C-C
bonds chain. Both the anisotropy and high stiffness of the nanographene
originate at the response of the benzenoid unit to stress.Comment: 19 pages, 7 figures 1 tabl
A fourfold coordinated point defect in silicon
Due to their technological importance, point defects in silicon are among the
best studied physical systems. The experimental examination of point defects
buried in bulk is difficult and evidence for the various defects usually
indirect. Simulations of defects in silicon have been performed at various
levels of sophistication ranging from fast force fields to accurate density
functional calculations. The generally accepted viewpoint from all these
studies is that vacancies and self interstitials are the basic point defects in
silicon. We challenge this point of view by presenting density functional
calculations that show that there is a new fourfold coordinated point defect in
silicon that is lower in energy
Raman scattering in C_{60} and C_{48}N_{12} aza-fullerene: First-principles study
We carry out large scale {\sl ab initio} calculations of Raman scattering
activities and Raman-active frequencies (RAFs) in
aza-fullerene. The results are compared with those of .
Twenty-nine non-degenerate polarized and 29 doubly-degenerate unpolarized RAFs
are predicted for . The RAF of the strongest Raman
signal in the low- and high-frequency regions and the lowest and highest RAFs
for are almost the same as those of .
The study of reveals the importance of electron correlations and
the choice of basis sets in the {\sl ab initio} calculations. Our best
calculated results for with the B3LYP hybrid density functional
theory are in excellent agreement with experiment and demonstrate the desirable
efficiency and accuracy of this theory for obtaining quantitative information
on the vibrational properties of these molecules.Comment: submitted to Phys.Rev.
First principles simulations of liquid Fe-S under Earth's core conditions
First principles electronic structure calculations, based upon density
functional theory within the generalized gradient approximation and ultra-soft
Vanderbilt pseudopotentials, have been used to simulate a liquid alloy of iron
and sulfur at Earth's core conditions. We have used a sulfur concentration of
wt, in line with the maximum recent estimates of the sulfur
abundance in the Earth's outer core. The analysis of the structural, dynamical
and electronic structure properties has been used to report on the effect of
the sulfur impurities on the behavior of the liquid. Although pure sulfur is
known to form chains in the liquid phase, we have not found any tendency
towards polymerization in our liquid simulation. Rather, a net S-S repulsion is
evident, and we propose an explanation for this effect in terms of the
electronic structure. The inspection of the dynamical properties of the system
suggests that the sulfur impurities have a negligible effect on the viscosity
of Earth's liquid core.Comment: 24 pages (including 8 figures
Efficient index handling of multidimensional periodic boundary conditions
An efficient method is described to handle mesh indexes in multidimensional
problems like numerical integration of partial differential equations, lattice
model simulations, and determination of atomic neighbor lists. By creating an
extended mesh, beyond the periodic unit cell, the stride in memory between
equivalent pairs of mesh points is independent of their position within the
cell. This allows to contract the mesh indexes of all dimensions into a single
index, avoiding modulo and other implicit index operations.Comment: 2 pages, 0 figure
First principles study of the origin and nature of ferromagnetism in (Ga,Mn)As
The properties of diluted GaMnAs are calculated for a wide range
of Mn concentrations within the local spin density approximation of density
functional theory. M\"ulliken population analyses and orbital-resolved
densities of states show that the configuration of Mn in GaAs is compatible
with either 3d or 3d, however the occupation is not integer due to the
large - hybridization between the Mn states and the valence band of
GaAs. The spin splitting of the conduction band of GaAs has a mean field-like
linear variation with the Mn concentration and indicates ferromagnetic coupling
with the Mn ions. In contrast the valence band is antiferromagnetically coupled
with the Mn impurities and the spin splitting is not linearly dependent on the
Mn concentration. This suggests that the mean field approximation breaks down
in the case of Mn-doped GaAs and corrections due to multiple scattering must be
considered. We calculate these corrections within a simple free electron model
and find good agreement with our {\it ab initio} results if a large exchange
constant (eV) is assumed.Comment: 15 pages, 14 figure
Phonons and related properties of extended systems from density-functional perturbation theory
This article reviews the current status of lattice-dynamical calculations in
crystals, using density-functional perturbation theory, with emphasis on the
plane-wave pseudo-potential method. Several specialized topics are treated,
including the implementation for metals, the calculation of the response to
macroscopic electric fields and their relevance to long wave-length vibrations
in polar materials, the response to strain deformations, and higher-order
responses. The success of this methodology is demonstrated with a number of
applications existing in the literature.Comment: 52 pages, 14 figures, submitted to Review of Modern Physic
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