Modeling radiative and non-radiative pathways at both the Franck-Condon and Herzberg-Teller approximation level.

Here, we present a concise model that can predict the photoluminescent properties of a given compound from first principles, both within and beyond the Franck-Condon approximation. The formalism required to compute fluorescence, Internal Conversion (IC), and Inter-System Crossing (ISC) is discussed. The IC mechanism, in particular, is a difficult pathway to compute due to difficulties associated with the computation of required bosonic configurations and non-adiabatic coupling elements. Here, we offer a discussion and breakdown on how to model these pathways at the Density Functional Theory (DFT) level with respect to its computational implementation, strengths, and current limitations. The model is then used to compute the photoluminescent quantum yield (PLQY) of a number of small but important compounds: anthracene, tetracene, pentacene, diketo-pyrrolo-pyrrole (DPP), and Perylene Diimide (PDI) within a polarizable continuum model. Rate constants for fluorescence, IC, and ISC compare well for the most part with respect to experiment, despite triplet energies being overestimated to a degree. The resulting PLQYs are promising with respect to the level of theory being DFT. While we obtained a positive result for PDI within the Franck-Condon limit, the other systems require a second order correction. Recomputing quantum yields with Herzberg-Teller terms yields PLQYs of 0.19, 0.08, 0.04, 0.70, and 0.99 for anthracene, tetracene, pentacene, DPP, and PDI, respectively. Based on these results, we are confident that the presented methodology is sound with respect to the level of quantum chemistry and presents an important stepping stone in the search for a tool to predict the properties of larger coupled systems.

Vacancy induced formation of nanoporous silicon, carbon and silicon carbide.

Nanoporous semiconductors are used in a range of applications from sensing and gas separation, to photovoltaics, rechargeable batteries, energetic materials and micro electro mechanical systems. In most cases porosity occurs in conjunction with the competing process of amorphisation, creating a complicated material that responds differently to strain and density changes, depending on the composition. In this paper we use simple computational workflow involving Monte Carlo simulation, numerical characterisation and statistical analysis to explore the development of amorphous and nanoporous carbon, silicon and silicon carbide. We show that amorphous regions in Si and SiC form in advance of nanopores, and are essential in stabilising the nanopores once developed. Carbon prefers a porous structure at lower strains than amorphisation and exhibits a bimodal change in the structure which correlates with the change in C-C bond angles from tetrahedral sp3-like bonds to hexagonal sp2-like bonds as the strain increases. These results highlight how both of these processes can be analysed simultaneously using reliable interatomic forcefields or density functionals, provided sufficient samples are included to support the statistics.

Hubbard physics in the PAW GW approximation.

It is demonstrated that the signatures of the Hubbard Model in the strongly interacting regime can be simulated by modifying the screening in the limit of zero wavevector in Projector-Augmented Wave GW calculations for systems without significant nesting. This modification, when applied to the Mott insulator CuO, results in the opening of the Mott gap by the splitting of states at the Fermi level into upper and lower Hubbard bands, and exhibits a giant transfer of spectral weight upon electron doping. The method is also employed to clearly illustrate that the M1 and M2 forms of vanadium dioxide are fundamentally different types of insulator. Standard GW calculations are sufficient to open a gap in M1 VO2, which arise from the Peierls pairing filling the valence band, creating homopolar bonds. The valence band wavefunctions are stabilized with respect to the conduction band, reducing polarizability and pushing the conduction band eigenvalues to higher energy. The M2 structure, however, opens a gap from strong on-site interactions; it is a Mott insulator.

Optical properties of a conjugated-polymer-sensitised solar cell: the effect of interfacial structure.

Dye-sensitised solar cells (DSSCs) have sparked considerable interest over two decades. Recently, a method of polymer-wire sensitisation was demonstrated; the polymer is suggested to form a hole transport pathway (wire) following initial charge separation. We predict the optical properties of this polymer in various interfacial configurations, including the effects of chain length and attachment to {100} or {101} TiO2 facets. Contrary to most DSSCs, the {100} facet model best describes the experimental spectrum, predicting a relative thickness of 5.7 ± 0.2 µm, although {101} attachment, if implemented, may improve collection efficiency. Long chains are optimal, and stable attachment sites show minimal differences to absorbance in the major solar emission (visible) band. Combinations of {100}, {101}, and pseudo-bulk TiO2 models in three-parameter fits to experiment confirm the relative importance of the {100} facet.

Ab Initio electronic properties of monolayer phosphorus nanowires in silicon.

Epitaxial circuitry offers a revolution in silicon technology, with components that can be fabricated on atomic scales. We perform the first ab initio calculation of atomically thin epitaxial nanowires in silicon, investigating the fundamental electronic properties of wires two P atoms thick, similar to those produced this year by Weber et al. For the first time, we catch a glimpse of disorder-related effects in the wires--a prerequisite for understanding real fabricated systems. Interwire interactions are made negligible by including 40 ML of silicon in the vertical direction (and the equivalent horizontally). Accurate pictures of band splittings and the electronic density are presented, and for the first time the effective masses of electrons in such device components are calculated.

Effect of nitrogen and intrinsic defect complexes on conversion efficiency of ZnO for hydrogen generation from water.

Band gap narrowing is important for applications of ZnO, especially for photoelectrochemical water splitting. In this work, we carried out first-principles electronic structure calculations with a hybrid density functional on defected ZnO. It is found that nitrogen substitutional doping alone cannot explain the largely enhanced conversion efficiency observed in nitrogen doped ZnO. Instead, complex defects formed by substitutional nitrogen and intrinsic defects play an important role in the band gap narrowing, in agreement with recent experimental results. We propose ZnO fabricated in a Zn-rich environment with heavy nitrogen doping as a photocatalyst for hydrogen generation from water splitting. A method for controlling the band gap of ZnO is also proposed.

A kinetic Monte Carlo study of Pt on Au(111) with applications to bimetallic catalysis.

Pt-decorated Au nanostructures and bimetallic PtAu nanoparticles have been shown to act as catalysts. Consequently we investigate the formation of extended Pt decorations of an Au island edge on Au(111) as possible catalysts. The investigation is by simulation using the kinetic Monte Carlo method. The effects of varying the rate of deposition of Pt atoms and the simulation temperature on the morphology of the resulting Pt nanostructures were investigated. The thickness and roughness of the nanostructures are readily influenced, with temperature being the more important factor. A combination of both high temperature and low deposition rate was the most effective at reducing the roughness. PtAu alloying in the Au island edge was identified. This work is (to the best of our knowledge) the first kinetic Monte Carlo simulation study of the formation of Pt nanostructures on Au. We demonstrate how the morphology of the Pt nanostructures can be controlled. The nanostructures studied here, comprising an adjustable mix of Pt overlayers and novel 1D PtAu surface alloys, are expected to be of considerable interest as potential bimetallic nano-catalysts.

Ab initio calculation of energy levels for phosphorus donors in silicon.

The s manifold energy levels for phosphorus donors in silicon are important input parameters for the design and modeling of electronic devices on the nanoscale. In this paper we calculate these energy levels from first principles using density functional theory. The wavefunction of the donor electron's ground state is found to have a form that is similar to an atomic s orbital, with an effective Bohr radius of 1.8 nm. The corresponding binding energy of this state is found to be 41 meV, which is in good agreement with the currently accepted value of 45.59 meV. We also calculate the energies of the excited 1s(T 2) and 1s(E) states, finding them to be 32 and 31 meV respectively.

First-principles modeling of dopants in C29 and C29H24 nanodiamonds.

Presented here is our continuing first-principles density functional theory study of the structural stability of a select group of dopants in diamond nanocrystals. On the basis of the work of others concerning dopants in diamond and endohedral atoms in fullerenes, the dopants selected for use here are oxygen, aluminum, silicon, phosphorus, and sulfur. These atoms were included substitutionally in the center of a 29-carbon-atom nanodiamond crystal, and each structure was relaxed using the Vienna Ab Initio Simulation Package. We describe the bonding and structure of the relaxed doped nanocrystals via examination of the electron charge density and point group symmetry. In combination with our previously reported results, it is anticipated that these results will assist in providing a better understanding of the mechanical stability of doped nanodiamonds for use in diamond nanodevices.

Simulation and bonding of dopants in nanocrystalline diamond.

The doping of the wide-band gap semiconductor diamond has led to the invention of many electronic and optoelectronic devices. Impurities can be introduced into diamond during chemical vapor deposition or high pressure-high temperature growth, resulting in materials with unusual physical and chemical properties. For electronic applications one of the main objectives in the doping of diamond is the production of p-type and n-type semiconductors materials; however, the study of dopants in diamond nanoparticles is considered important for use in nanodevices, or as qubits for quantum computing. Such devices require that bonding of dopants in nanodiamond must be positioned substitutionally at a lattice site, and must exhibit minimal or no possibility of diffusion to the nanocrystallite surface. In light of these requirements, a number of computational studies have been undertaken to examine the stability of various dopants in various forms of nanocrystalline diamond. Presented here is a review of some such studies, undertaken using quantum mechanical based simulation methods, to provide an overview of the crystal stability of doped nanodiamond for use in diamondoid nanodevices.

Bucky-wires and the instability of diamond (111) surfaces in one-dimension.

Recent advances in the fabrication and characterization of semiconductor and metallic nanowires are meeting the high expectations of nanotechnolgists. Although diamond has remarkable electronic and chemical properties, development of diamond nanowires has been slow, while the development of carbon nanotube-based technologies continues at a furious pace. Recently, the theoretical and experimental observation of the transformation of nanodiamonds into carbon-onions (and vice versa) has led to a new intermediate phase of carbon, denoted "bucky diamond", with a diamond core encased in an carbon onion-like shell. These findings lead to the question of whether a similar transformation occurs in diamond nanowires. We used ab initio techniques to determine the relaxed structure of diamond nanowires with octahedral surface facets, with results exhibiting delamination of octahedral surfaces, and indicating the formation of "bucky-wires". The effects of surface hydrogenation upon this transition also is examined.

Long-time behavior of the velocity autocorrelation function for moderately dense, soft-repulsive, and Lennard-Jones fluids.

The long-time behavior of the velocity autocorrelation function (VAF), for hard disk and sphere systems, has been extensively explored. Its behavior for systems interacting via a soft repulsive or attractive potential is less well known. We explore the conditions under which the nonexponential, long-time tail in the velocity autocorrelation function of a tagged atom, in soft-repulsive sphere (Weeks-Chandler-Andersen) and Lennard-Jones atomic fluids, may be readily observed by the molecular dynamics method. The effect of changing the system size, the fluid density, the form of the interatomic force and the mass of the tagged atoms are investigated. We were able to observe this long-time tail only for systems of moderate density. At low density the effect, if it exists, is at longer times than we can currently simulate owing to limitations of system size and at higher densities these tails were not observed possibly due to other effects dominating the behavior of the VAF and masking this behavior. Under the physical conditions that are simulated here attractive forces have very little effect on the behavior of the VAF. However, as the mass of the tagged particles is increased the time at which the long-time tail commences is lengthened and its magnitude is significantly increased. This later effect suggests that by increasing the mass of the tagged particles one may be able to study more readily the behavior, nature and physical origin of long-time behavior of the VAF both by computational and by experimental techniques.

Benchmarking the dental implant evidence on MEDLINE.

The purpose of this study was to estimate the quantity of dental implant literature available on MEDLINE for evidence-based clinical decision-making and to identify its location. A search strategy based on Medical Subject Headings for dental implants was developed to examine MEDLINE using the Ovid Web Gateway search engine. Sensitive and specific methodologic search filters identified 4 categories of information: etiology, diagnosis, therapy, and prognosis. The results were then subdivided by year to identify trends and sorted to identify the sources of publications. The searches identified 4,655 articles published in English between 1989 and 1999 on human dental implants on MEDLINE. The mean number of articles (+/- SD) per year ranged from 15 +/- 11 for specific searches to 107 +/- 50 for sensitive searches. The number of articles increased by 14% to 43% each year for the sensitive search. When subdivided by clinical category, the mean numbers of articles per year for sensitive and specific searches were, respectively: diagnosis 12 +/- 7.5 and 1.5 +/- 1.6, etiology 58 +/- 33 and 1.9 +/- 2.5, therapy 23 +/- 15 and 0.3 +/- 0.5, and prognosis 67 +/- 33 and 12 +/- 8.3. Four dental journals account for approximately half of these publications. These results provide 6 key central findings: (1) there appears to be a substantial literature of clinically relevant information on implants upon which to base clinical decisions; (2) the implant literature is significantly biased toward articles addressing prognosis; (3) to stay current, one would need to read between 1 and 2 articles per week 52 weeks per year, and this number increases significantly each year; (4) approximately 50% of the articles were published in 4 journals, whereas the remainder reside in approximately 97 other journals, making it difficult to stay current; (5) these trends reaffirm the need for lifelong learning; (6) these trends also suggest the need for computer-based clinical knowledge systems.

Morphological and phase stability of zinc blende, amorphous and mixed core-shell ZnS nanoparticles.

Zinc sulfide (ZnS) nanoparticles are of interest for their luminescent and catalytic properties which are being considered for the next generation of optical, electronic and photovoltaic devices. However, ZnS nanoparticles undergo reversible and irreversible phase transformations under ambient conditions, so a detailed understanding of the nanomorphology is critical in ensuring these desirable properties can be controlled and maintained. Anticipating the structure and transformations in ZnS nanoparticles experimentally is difficult, since selectivity among competing phases, shapes and sizes is intrinsically linked. Presented here are the results of first principle computer simulations and advanced theoretical modelling used to investigate the relationship between size and shape in determining the crystallinity of ZnS nanoparticles. We find that the equilibrium morphology is characterised by {220} facets, irrespective of the size of the particle, but that the presence of different high energy facets introduced kinetically may significantly influence the zinc blende to amorphous ZnS transformation size, as well as the agglomeration behaviour. In addition to this, we model the relationship between transformation size, morphology and the ratio of crystalline core to amorphous shell and show that at small sizes, a core-shell crystalline/amorphous structure is thermodynamically favourable.

Quantum Monte Carlo calculations of the potential energy curve of the helium dimer.

We report results of two quantum Monte Carlo methods -- variational Monte Carlo and diffusion Monte Carlo -- on the potential energy curve of the helium dimer. In contrast to previous quantum Monte Carlo calculations on this system, we have employed trial wave functions of the Slater-Jastrow form and used the fixed node approximation for the fermion nodal surface. We find both methods to be in excellent agreement with the best theoretical results at short range. In addition, the diffusion Monte Carlo results give very good agreement across the whole potential energy curve, while the Slater-Jastrow wave function fails to bind the dimer at all.