Permanent excimer superstructures by supramolecular networking of metal quantum clusters.

Excimers are evanescent quasi-particles that typically form during collisional intermolecular interactions and exist exclusively for their excited-state lifetime. We exploited the distinctive structure of metal quantum clusters to fabricate permanent excimer-like colloidal superstructures made of ground-state noninteracting gold cores, held together by a network of hydrogen bonds between their capping ligands. This previously unknown aggregation state of matter, studied through spectroscopic experiments and ab initio calculations, conveys the photophysics of excimers into stable nanoparticles, which overcome the intrinsic limitation of excimers in single-particle applications-that is, their nearly zero formation probability in ultra-diluted solutions.

Ligand Induced Spectral Changes in CdSe Quantum Dots.

The rational design of ligand molecules has earned lots of attention as an elegant means to tailor the electronic and optical properties of semiconductor quantum dots (QDs). Aromatic dithiocarbamate molecules, in particular, are known to greatly influence the optoelectronic properties of CdSe QDs, red-shifting the absorption features and enhancing the photoluminescence. Here, we present an integrated computational study, which combines ab initio molecular dynamics and excited state calculations including thousands of excitations, aimed at understanding the impact of this kind of surface ligand on the optoelectronic properties of CdSe QDs.

Photoinduced Energy Shift in Quantum-Dot-Sensitized TiO2: A First-Principles Analysis.

We investigate the photoinduced dipole (PID) phenomenon, which holds enormous potential for the optimization of quantum dot-sensitized solar cells (QDSSCs), by means of first-principles electronic structure calculations. We demonstrate that the sensitization of the TiO2 substrate with core/shell QDs produces almost no changes in the ground state but decisively improves the performance upon photoexcitation. In particular, the maximum attainable VOC is predicted to increase by ∼25 meV due to two additive effects: (i) the displacement of the photoexcited hole away from the TiO2 surface and (ii) the interfacial electrostatic interaction established between the TiO2-injected electrons and the holes residing in the QD core.

A hierarchical algorithm for molecular similarity (H-FORMS).

A new hierarchical method to determine molecular similarity is introduced. The goal of this method is to detect if a pair of molecules has the same structure by estimating a rigid transformation that aligns the molecules and a correspondence function that matches their atoms. The algorithm firstly detect similarity based on the global spatial structure.

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations.

The effect of TiO2 surface on the electron injection efficiency in PbS quantum dot solar cells: a first-principles study.

We present a density functional theory (DFT) study aimed at understanding the injection and recombination processes that occur at the interface between PbS QDs and TiO2 oxide nanoparticles with different morphologies. The calculated injection rates fall in the picosecond timescale in good agreement with the experiments. In addition, our simulations show that the (101) facet of TiO2 more favourably accommodates the QD, resulting in stronger electronic couplings and faster electron injections than the (001) surfaces.

Epitaxially connected PbSe quantum-dot films: controlled neck formation and optoelectronic properties.

Ligand exchange is a much-used method to increase the conductivity of colloidal quantum-dot films by replacing long insulating ligands on quantum-dot surfaces with shorter ones. Here we show that while some ligands indeed replace the original ones as expected, others may be used to controllably remove the native ligands and induce epitaxial necking of specific crystal facets. In particular, we demonstrate that amines strip lead oleate from the (100) surfaces of PbSe quantum dots.

CdS nanoclusters doped with divalent atoms.

ZnS and CdS small nanoclusters have been predicted to trap alkali metals and halogen atoms. However would this kind of nanocompounds be able to encapsulate dianions and dications? This would be very interesting from an experimental point of view, since it would allow the isolation of such divalent ions. Moreover, the resulting endohedral complexes would serve as building blocks for new cluster-assembled materials, with enhanced stability arising from the electrostatic interaction between the incarcerated ions.

Carbo-cages: a computational study.

Inspired by their geometrical perfection, intrinsic beauty, and particular properties of polyhedranes, a series of carbo-cages is proposed in silico via density functional theory computations. The insertion of alkynyl units into the C-C bonds of polyhedranes results in a drastic lowering of the structural strain. The induced magnetic field shows a significant delocalization around the three-membered rings.

DFT/TDDFT study of the adsorption of N3 and N719 dyes on ZnO(101̅0) surfaces.

ZnO has attracted a great deal of research as a potential replacement of TiO2 for dye-sensitized solar cells (DSSCs), owing to the unique combination of interesting electronic properties (i.e., high electron mobility) and structural richness.

Benchmark Assessment of Density Functional Methods on Group II-VI MX (M = Zn, Cd; X = S, Se, Te) Quantum Dots.

In this work, we build a benchmark data set of geometrical parameters, vibrational normal modes, and low-lying excitation energies for MX quantum dots, with M = Cd, Zn, and X = S, Se, Te. The reference database has been constructed by ab initio resolution-of-identity second-order approximate coupled cluster RI-CC2/def2-TZVPP calculations on (MX)6 model molecules in the wurtzite structure. We have tested 26 exchange-correlation density functionals, ranging from local generalized gradient approximation (GGA) and hybrid GGA to meta-GGA, meta-hybrid, and long-range corrected.

A DFT/TDDFT study on the optoelectronic properties of the amine-capped magic (CdSe)13 nanocluster.

Motivated by the recent experiments by Wang et al. (Angew. Chem.

Heavy periodane.

The potential energy surface of the hypothetical NaMgAlSiPSCl system (heavy periodane) is exhaustively analyzed via the gradient embedded genetic algorithm (GEGA) in combination with density functional theory (DFT) computations. The electronegativity differences among the elements in both the second and third rows of the periodic table indicate that low-energy heavy periodane structures are obtained when highly electronegative and electropositive elements are bound together, but the global minimum of the heavy periodane system is completely different to its second-row analog (LiBeBCNOF).