9,876 research outputs found
Steric engineering of metal-halide perovskites with tunable optical band gaps
Owing to their high energy-conversion efficiency and inexpensive fabrication
routes, solar cells based on metal-organic halide perovskites have rapidly
gained prominence as a disruptive technology. An attractive feature of
perovskite absorbers is the possibility of tailoring their properties by
changing the elemental composition through the chemical precursors. In this
context, rational in silico design represents a powerful tool for mapping the
vast materials landscape and accelerating discovery. Here we show that the
optical band gap of metal-halide perovskites, a key design parameter for solar
cells, strongly correlates with a simple structural feature, the largest
metal-halide-metal bond angle. Using this descriptor we suggest continuous
tunability of the optical gap from the mid-infrared to the visible. Precise
band gap engineering is achieved by controlling the bond angles through the
steric size of the molecular cation. Based on these design principles we
predict novel low-gap perovskites for optimum photovoltaic efficiency, and we
demonstrate the concept of band gap modulation by synthesising and
characterising novel mixed-cation perovskites.Comment: This manuscript was submitted for publication on March 6th, 2014.
Many of the results presented in this manuscript were presented at the
International Conference on Solution processed Semiconductor Solar Cells,
held in Oxford, UK, on 10-12 September 2014. The manuscript is 37 pages long
and contains 8 figure
Role of electronic localization in the phosphorescence of iridium sensitizing dyes
In this work we present a systematic study of three representative iridium
dyes, namely, Ir(ppy)3, FIrpic and PQIr, which are commonly used as sensitizers
in organic optoelectronic devices. We show that electronic correlations play a
crucial role in determining the excited-state energies in these systems, due to
localization of electrons on Ir d orbitals. Electronic localization is captured
by employing hybrid functionals within time-dependent density-functional theory
(TDDFT) and with Hubbard-model corrections within the delta-SCF approach. The
performance of both methods are studied comparatively and shown to be in good
agreement with experiment. The Hubbard-corrected functionals provide further
insight into the localization of electrons and on the charge-transfer character
of excited-states. The gained insight allows us to comment on envisioned
functionalization strategies to improve the performance of these systems.
Complementary discussions on the delta-SCF method are also presented in order
to fill some of the gaps in the literature.Comment: 15 pages, 14 figure
Broken-Symmetry Unrestricted Hybrid Density Functional Calculations on Nickel Dimer and Nickel Hydride
In the present work we investigate the adequacy of broken-symmetry
unrestricted density functional theory (DFT) for constructing the potential
energy curve of nickel dimer and nickel hydride, as a model for larger bare and
hydrogenated nickel cluster calculations. We use three hybrid functionals: the
popular B3LYP, Becke's newest optimized functional Becke98, and the simple
FSLYP functional (50% Hartree-Fock and 50% Slater exchange and LYP
gradient-corrected correlation functional) with two basis sets: all-electron
(AE) Wachters+f basis set and Stuttgart RSC effective core potential (ECP) and
basis set.
We find that, overall, the best agreement with experiment, comparable to that
of the high-level CASPT2, is obtained with B3LYP/AE, closely followed by
Becke98/AE and Becke98/ECP. FSLYP/AE and B3LYP/ECP give slightly worse
agreement with experiment, and FSLYP/ECP is the only method among the ones we
studied that gives an unaceptably large error, underestimating the dissociation
energy of nickel dimer by 28%, and being in the largest disagreement with the
experiment and the other theoretical predictions.Comment: 17 pages, 7 tables, 7 figures; submitted to J. Chem. Phys.;
Revtex4/LaTeX2e. v2 (8/5/04): New (and better) ECP results, without charge
density fitting (which was found to give large errors). Subtracted the
relativistic corrections from all experimental value
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