Studio teorico di proprieta' di nanoparticelle con l'uso del modello "jellium" in approssimazione Hartree-Fock Ristretta

In questo lavoro di tesi abbiamo effettuato calcoli di polarizabilità su cluster metallici di dimensioni variabili in approssimazione Time Dependent Hartree Fock (TDHF) ed MP2. Il modello utilizzato è quello di una scatola cubica in cui la carica positiva è approssimato da un jellium uniforme. Per ogni atomo del cluster viene considerato solo il comportamento delgli elettroni più esterni, che possono muoversi su di un volume predefinito, maggiore o uguale a quello occupato dal cluster per tenere conto degli effetti di spill out. Particolare enfasi è posta all'uso delle simmetrie del sistema cubico per ottimizzare la soluzione del problema

Emergence of hidden phases of methylammonium lead-iodide (CH3_3NH3_3PbI3_3) upon compression

We perform a thorough structural search with the minima hopping method (MHM) to explore low-energy structures of methylammonium lead iodide. By combining the MHM with a forcefield, we efficiently screen vast portions of the configurational space with large simulation cells containing up to 96 atoms. Our search reveals two structures of methylammonium iodide perovskite (MAPI) that are substantially lower in energy than the well-studied experimentally observed low-temperature $Pnma$ orthorhombic phase according to density functional calculations. Both structures have not yet been reported in the literature for MAPI, but our results show that they could emerge as thermodynamically stable phases via compression at low temperatures. In terms of the electronic properties, the two phases exhibit larger band gaps than the standard perovskite-type structures. Hence, pressure induced phase selection at technologically achievable pressures (i.e., via thin-film strain) is a route towards the synthesis of several MAPI polymorph with variable band gaps

A computational analysis of the vibrational absorption of molecular solids in the teraherz range

In this thesis, we deal with the application of transmission terahertz spectroscopy as an analysis tool for the study of molecular solids, in particular organic crystals of pharmaceutical interest. Most of the work has been performed using two computational packages aimed at the interpretation of the spectra, one based on molecular forcefields (DMACRYS), the other on solid state density functional theory (CASTEP). We compare low temperature determinations of several molecular organic crystals to calculated spectra, and attempt to assign calculated modes of vibrations to absorption peaks, based on the similarity in frequency between the measured and calculated peaks. One of the main aims of this work is to establish the limits of our forcefield approach, which is based on the approximation that the intramolecular degrees of freedom can be neglected. We analyse the normal modes of vibration calculated with CASTEP, evaluating the amount of rigid molecule rotational and translational contribution to each eigenvector as a function of frequency, in order to validate our forcefield approach. We also compare the two sets of eigenvectors from the DMACRYS and CASTEP calculations to assess the similarity between the two approaches. We perform the same eigenvectors analysis on several hydrate systems in order to understand the role of water in the lattice dynamics of crystalline hydrates. We attempt a classification of the eigenvectors based on the strength of the forces involved in the molecular vibrations and based on the amount of the water contribution to each normal mode. A set of isostructural crystals is analysed in order to understand the effect that small variations (in the molecular formula and in the unit cell arrangement) have on the measured and calculated absorption spectra of a crystal. Finally, we discuss the use and development of computational methods that allow us to have a more realistic description of the molecular electrostatic in DMACRYS.This work was supported by Astra Zenec

Emergence of hidden phases of methylammonium lead iodide (CH3NH3PbI3) upon compression

We perform a thorough structural search with the minima hopping method (MHM) to explore low-energy structures of methylammonium lead iodide. By combining the MHM with a forcefield, we efficiently screen vast portions of the configurational space with large simulation cells containing up to 96 atoms. Our search reveals two structures of methylammonium iodide perovskite (MAPI) that are substantially lower in energy than the well-studied experimentally observed low-temperature Pnma orthorhombic phase according to density functional calculations. Both structures have not yet been reported in the literature for MAPI, but our results show that they could emerge as thermodynamically stable phases via compression at low temperatures. In terms of the electronic properties, the two phases exhibit larger band gaps than the standard perovskite-type structures. Hence, the pressure-induced phase selection at technologically achievable pressures (i.e., via thin-film strain) is a viable route towards the synthesis of several MAPI polymorph with variable band gaps

Emergency Mosquito Control on a Selected Area in Eastern North Carolina After Hurricane Irene

Natural disasters such as hurricanes may contribute to mosquito abundance and, consequently, arbovirus transmission risk. In 2011, flooding from Hurricane Irene in eastern North Carolina (NC) resulted in increased mosquito populations that hindered recovery efforts. Budget shortfalls in NC have reduced the functionality of long-term mosquito surveillance and control programs; hence, many counties rely on the Federal Emergency Management Agency for post-disaster mosquito control. This pilot study examines mosquito abundance pre- and post-aerial insecticide spraying at eight study sites in Washington and Tyrrell Counties in rural eastern NC after Hurricane Irene. Percent change was calculated and compared for traps in areas that received aerial pesticide application and those that did not. Traps in spray zones show decreases in mosquito abundance when compared to control traps (treatment: −52.93%; control: 3.55%), although no significant differences (P = 0.286) were found in mosquito abundance between groups. Implications of reactive rather than proactive mosquito control responses are discussed

Experimental and theoretical studies of tetramethoxy-p-benzoquinone: infrared spectra, structural and lithium insertion properties

International audienceIn the search for low-polluting electrode materials for batteries, the use of redox-active organic compounds represents a promising alternative to conventional metal-based systems. In this article we report a combined experimental and theoretical study of tetramethoxy-p-benzoquinone (TMQ). In carbonate-based electrolytes, electrochemical behaviour of this compound is characterized by a reversible insertion process located at approximately 2.85 V vs. Li+/Li0. This relatively high potential reactivity, coupled with our effort to develop computational methodologies in the field of organic electrode materials, prompted us to complement these experimental data with theoretical studies performed using density functional theory (DFT). Single crystals of TMQ were synthesized and thoroughly characterized showing that this quinonic species crystallised in the P21/n space group. The experimental crystal structure of TMQ was then used to assess various DFT methods. The structural features and vibrational spectra were thus predicted by using as a whole five common density functionals (PBE, LDA, revPBE, PBEsol, B3PW91) with and without a semi-empirical correction to account for the van der Waals interactions using either Grimme's (DFT-D2) or Tkatchenko-Scheffler (TS) scheme. The most reliable combination of the DFT functional and the explicit dispersion correction was chosen to study the Li-intercalated molecular crystal (LiTMQ) with the view of indentifying Li insertion sites. A very close agreement with the experiment was found for the average voltage by using the most stable relaxed hypothetical LiTMQ structure. Additionally, a comparison of vibrational spectra gained either for TMQ molecule and its dimer in gas phase or through periodic calculation was undertaken with respect to the experimentally measured infrared spectra. The topological features of the bonds were also investigated in conjunction with estimates of net atomic charges to gain insight into the effect of chemical bonding and intermolecular interaction on Li intercalation. Finally, π-electron delocalization of both quinone and alkali salts of p-semiquinone were determined using the Harmonic Oscillator model of Aromaticity (HOMA) or aromatic fluctuation index (FLU) calculations

Climate Variability, Social and Environmental Factors, and Ross River Virus Transmission: Research Development and Future Research Needs

Background: Arbovirus diseases have emerged as a global public health concern. However, the impact of climatic, social and environmental variability on the transmission of arbovirus diseases remains to be determined. Objective: We provided an overview of research development and future research directions about the inter-relationship between climate variability, social and environmental factors and the transmission of Ross River virus (RRV) – the most common and widespread arbovirus disease in Australia. Methods: We conducted a systematic literature search on climatic, social and environmental factors and RRV disease. Potentially relevant studies were identified from a series of electronic searches. Databases searched were the MEDLINE (via EBSCOhost), Current Contents Connect (via ISI Web of Knowledge) and ScienceDirect. We critically reviewed key predictors of RRV transmission through an integration of our own research with literature. Results: The body of evidence reveals that the transmission cycles of RRV disease appeared to be sensitive to climate variability. Rainfall, temperature and high tides were among major determinants of the transmission of RRV disease at macro level. However, the nature and magnitude of the inter-relationship between climate variability, mosquito density and the transmission of RRV disease varied with geographic area and socio-environmental condition. Projected anthropogenic global climatic change may result in an increase in RRV infections. Conclusions: The analysis indicates that there is a complex relationship between climate variability, social and environmental factors and Ross River virus transmission. Different strategies should be adopted for the control and prevention of Ross River virus disease at different levels. These research findings could be used as an additional tool to support decision-making in disease control/surveillance and risk management

Maximum volume simplex method for automatic selection and classification of atomic environments and environment descriptor compression

Fingerprint distances, which measure the similarity of atomic environments, are commonly calculated from atomic environment fingerprint vectors. In this work, we present the simplex method that can perform the inverse operation, i.e., calculating fingerprint vectors from fingerprint distances. The fingerprint vectors found in this way point to the corners of a simplex. For a large dataset of fingerprints, we can find a particular largest simplex, whose dimension gives the effective dimension of the fingerprint vector space. We show that the corners of this simplex correspond to landmark environments that can be used in a fully automatic way to analyze structures. In this way, we can, for instance, detect atoms in grain boundaries or on edges of carbon flakes without any human input about the expected environment. By projecting fingerprints on the largest simplex, we can also obtain fingerprint vectors that are considerably shorter than the original ones but whose information content is not significantly reduced