84 research outputs found
Simulating Dye-Sensitized TiO2 Heterointerfaces in Explicit Solvent: Absorption Spectra, Energy Levels, and Dye Desorption
Dye-sensitized solar cells (DSCs) represent a valuable,
efficient, and low-cost alternative to conventional semiconductor
photovoltaic devices. A deeper understanding of the dye/semiconductor
heterointerface and of the dye-sensitized semiconductor/
electrolyte interactions are fundamental for further progress in
DSC technology. Here we report an ab initio molecular dynamics
simulation of a dye-sensitized TiO2 heterointerface “immersed” in an
explicit water environment for an efficient organic dye, followed by
TDDFT excited state calculations of the coupled dye/semiconductor/
solvent system. This new computational protocol and the extended model system allows us to gain unprecedented insight into
the excited state changes occurring for the solvated dye-sensitized heterointerface at room temperature, and to provide an atomistic
picture of water-mediated dye desorption
A well-scaling natural orbital theory
We introduce an energy functional for ground-state electronic structure
calculations. Its variables are the natural spin-orbitals of singlet many-body
wave functions and their joint occupation probabilities deriving from
controlled approximations to the two-particle density matrix that yield
algebraic scaling in general, and Hartree-Fock scaling in its seniority-zero
version. Results from the latter version for small molecular systems are
compared with those of highly accurate quantum-chemical computations. The
energies lie above full configuration interaction calculations, close to doubly
occupied configuration interaction calculations. Their accuracy is considerably
greater than that obtained from current density-functional theory
approximations and from current functionals of the one-particle density matrix.Comment: http://www.pnas.org/cgi/doi/10.1073/pnas.1615729113. arXiv admin
note: text overlap with arXiv:1309.392
Why are MoS2 monolayers not a good catalyst for the oxygen evolution reaction?
We use density functional theory based calculations to study the energetics of the oxygen evolution reaction on a monolayer of MoS2. This material, a prototypical example of a layered transition metal dichalcogenide, is intensely studied in the context of many important catalytical applications, in particular for the hydrogen evolution reaction. The second half-reaction of the water-splitting process, the oxygen evolution reaction, is almost never considered on this material, due to its low activity. Based on our calculations, we explain this experimentally observed poor catalytic activity for the oxygen evolution by the weak binding of two key reaction intermediates (hydroxyl and hydroperoxyl) to the substrate. We explore substitutional doping with oxygen and phosphorous as means to facilitate the oxygen evolution on MoS2 layers. The oxygen substitution slightly increases the reaction´s overpotential, but does not significantly change the energetics. The doping with phosphorous, on the other hand, is not a promising way to promote the oxygen evolution on MoS2 layers. We also explore the role of the edges of MoS2 layers. We find that while the adsorption energies of reaction intermediates are strongly influenced by the presence of an edge, the final reaction overpotential remains nearly the same as on a pristine monolayer, meaning that the presence of edges is not favoring the OER.Fil: German, Estefania. Universidad de Valladolid; España. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - BahĂa Blanca. Instituto de FĂsica del Sur. Universidad Nacional del Sur. Departamento de FĂsica. Instituto de FĂsica del Sur; ArgentinaFil: Gebauer, Ralph. The Abdus Salam. International Centre for Theoretical Physics; Itali
Density-functional perturbation theory goes time-dependent
The scope of time-dependent density-functional theory (TDDFT) is limited to the lowest portion of the spectrum of rather small systems (a few tens of atoms at most). In the static regime, density-functional perturbation theory (DFPT) allows one to calculate response functions of systems as large as currently dealt with in ground-state simulations. In this paper we present an effective way of combining DFPT with TDDFT. The dynamical polarizability is first expressed as an off-diagonal matrix element of the resolvent of the Kohn-Sham Liouvillian super-operator. A DFPT representation of response functions allows one to avoid the calculation of unoccupied Kohn-Sham orbitals. The resolvent of the Liouvillian is finally conveniently evaluated using a newly developed non-symmetric Lanczos technique, which allows for the calculation of the entire spectrum with a single Lanczos recursion chain. Each step of the chain essentially requires twice as many operations as a single step of the iterative diagonalization of the unperturbed Kohn-Sham Hamiltonian or, for that matter, as a single time step of a Car-Parrinello molecular dynamics run. The method will be illustrated with a few case molecular applications
Solution of the Bethe-Salpeter equation without empty electronic states: Application to the absorption spectra of bulk systems
An approach recently developed to solve the Bethe-Salpeter equation within density matrix perturbation theory is extended to the calculation of optical spectra of periodic systems. This generalization requires numerical integrations within the first Brillouin zone that are efficiently performed by exploiting point group symmetries. The technique is applied to the calculation of the optical spectra of bulk Si, diamond C, and cubic SiC. Numerical convergence and the accuracy of the Tamm-Dancoff approximation are discussed in detail
Turbo charging time-dependent density-functional theory with Lanczos chains
We introduce a new implementation of time-dependent density-functional theory
which allows the \emph{entire} spectrum of a molecule or extended system to be
computed with a numerical effort comparable to that of a \emph{single} standard
ground-state calculation. This method is particularly well suited for large
systems and/or large basis sets, such as plane waves or real-space grids. By
using a super-operator formulation of linearized time-dependent
density-functional theory, we first represent the dynamical polarizability of
an interacting-electron system as an off-diagonal matrix element of the
resolvent of the Liouvillian super-operator. One-electron operators and density
matrices are treated using a representation borrowed from time-independent
density-functional perturbation theory, which permits to avoid the calculation
of unoccupied Kohn-Sham orbitals. The resolvent of the Liouvillian is evaluated
through a newly developed algorithm based on the non-symmetric Lanczos method.
Each step of the Lanczos recursion essentially requires twice as many
operations as a single step of the iterative diagonalization of the unperturbed
Kohn-Sham Hamiltonian. Suitable extrapolation of the Lanczos coefficients
allows for a dramatic reduction of the number of Lanczos steps necessary to
obtain well converged spectra, bringing such number down to hundreds (or a few
thousands, at worst) in typical plane-wave pseudopotential applications. The
resulting numerical workload is only a few times larger than that needed by a
ground-state Kohn-Sham calculation for a same system. Our method is
demonstrated with the calculation of the spectra of benzene, C
fullerene, and of chlorofyll a.Comment: 15 pages, 7 figures, to be pdflatex + bibte
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