Structure, solvation, thermodynamics and fragmentation of molecular clusters

Cette thèse vise à étudier en détail le comportement d'agrégats moléculaires complexes et se concentre sur deux aspects principaux. Tout d'abord, la description des isomères de faible énergie des clusters d'ammonium et ammoniac et (H2O)1-7,11,12UH+ à travers l'exploration des surfaces d'énergie potentielle (PES) en utilisant une combinaison d'approches d'optimisation globales et locales. Les propriétés structurelles, de solvatation et thermodynamiques des isomères de basse énergie nouvellement identifiés ont été caractérisées. Par la suite, des simulations dynamiques de la dissociation induite par collision des (H2O)1-7,11,12UH+ et Py2+ ont été réalisées et analysées en termes de : mécanisme de dissociation, répartition d'énergie, spectres de masse et sections efficaces de collision pour complémenter des mesures expérimentales récentes menées sur ces espèces. L'optimisation globale des clusters (H2O)1-10NH4+ et (H2O)1-10NH3 a été réalisée au niveau de théorie SCC-DFTB (pour self-consistent-charge density-functional based tight-binding), pour laquelle des paramètres N-H améliorés ont été proposés, en combinaison avec l'approche d'exploration PTMD (pour parallel-tempering molecular dynamics). Les isomères de basse énergie nouvellement déterminés ont été optimisés au niveau MP2 afin d'évaluer la fiabilité de nos paramètres N-H modifiés. Les structures et les énergies de liaison obtenues avec la méthode SCC-DFTB sont en très bon accord avec les résultats de niveau MP2/Def2TZVP, ce qui démontre la capacité de l'approche SCC-DFTB à décrire la PES de ces espèces moléculaires et représente ainsi une première étape vers la modélisation d'agrégats complexes d'intérêt atmosphérique. L'intérêt porté aux (H2O)1-7,11,12UH+ vise à fournir une description détaillée d'expériences récentes de dissociation induite par collision (CID). Premièrement, les isomères stables des (H2O)1-7,11,12UH+ sont calculés en utilisant la même méthodologie que celle décrite ci-dessus. Ensuite, des simulations dynamiques des collisions entre isomères (H2O)1-7,11,12UH+ et un atome d'argon sont réalisées à énergie de collision constante au niveau SCC-DFTB. La proportion simulée d'agrégats neutres contenant l'uracile par rapport à celle d'agrégats chargés contenant l'uracile, la section efficace de fragmentation ainsi que les spectres de masse sont cohérents avec les données expérimentales ce qui met en évidence la précision de nos simulations. Ces dernières permettent de sonder en details les fragments qui se forment aux temps courts et de rationaliser la localisation du proton en excès sur ces fragments. Cette dernière propriété est fortement influencée par la nature de l'agrégat soumis à la collision. L'analyse de la proportion des fragments en fonction du temps et des spectres de masse démontrent que, jusqu'à 7 molécules d'eau, un mécanisme de dissociation direct alors que pour 11,12 molécules, un mécanisme statistique est plus susceptible d'intervenir. Enfin, des simulations d'expériences CID du Py2+ à différentes énergies de collision, entre 2,5 et 30 eV, sont présentées. Les simulations permettent de comprendre les processus de dissociation mis en jeu. L'accord entre les spectres de masse simulés et mesurés suggère que les principaux processus sont bien pris en compte par cette approche. Il semble que la majeure partie de la dissociation se produise sur une courte échelle de temps (moins de 3 ps). L'analyse de la répartition d'énergie cinétique est utilisée pour obtenir des informations sur les processus de collision/dissociation à l'échelle atomique. Les spectres de masse simulés des clusters parents et dissociés sont obtenus à partir en combinant simulations de dynamique moléculaire et théorie de l'espace des phases pour traiter respectivement la dissociation aux courtes et longues échelles de temps.This thesis aims at studying in details the behavior of complex molecular clusters and focuses on two main aspects. First, the description of low-energy isomers of ammonium/ammonia water clusters and (H2O)1-7,11,12UH+ through an extensive exploration of potential energy surfaces (PES) using a combination of global and local optimization schemes. Structural, solvation and thermodynamics properties of the newly identified low-energy isomers were characterized. Second, the dynamical simulations of collision-induced dissociation of (H2O)1-7,11,12UH+ and Py2+ were carried out to explore collision trajectories, dissociation mechanism, energy partition, mass spectra, and collision cross sections to complement experimental measurements conducted on these species. Global optimization of (H2O)1-10NH4+ and (H2O)1-10NH3 clusters is conducted at the self-consistent-charge density-functional based tight-binding (SCC-DFTB) level of theory, for which improved N-H parameters are proposed, in combination with the parallel-tempering molecular dynamics (PTMD) approach. Low-energy isomers of (H2O)1-10NH4+ and (H2O)1-10NH3 are further optimized at MP2 level in order to evaluate the reliability of our modified N-H parameters. Both structures and binding energies obtained at SCC-DFTB agree with the results at MP2/Def2TZVP level, which demonstrates the ability of SCC-DFTB to describe the PES of molecular species and represents a first step towards the modeling of complex aggregates of atmospheric interest. Focus on (H2O)1-7,11,12UH+ aims at providing a detailed description of recent collision-induced dissociation (CID) experiments. First, stable isomers of (H2O)1-7,11,12UH+ are calculated using the same methodology as described above. Then, dynamical simulations of the collisions between various (H2O)1-7,11,12UH+ isomers and argon is conducted at a constant collision energy at the SCC-DFTB level. Simulated proportion of formed neutral vs. protonated uracil containing clusters, fragmentation cross-section as well as mass spectra are consistent with the experimental data which highlights the accuracy of our simulations. They allow to probe which fragments are formed on the short time scale and rationalize the location of the excess proton on these fragments. This latter property is highly influenced by the nature of the aggregate undergoing the collision. Analyses of proportion of time-dependent fragments and mass spectra demonstrate that, up to 7 water molecules, a shattering mechanism occurs after collision whereas for n=11,12 a statistical mechanism is more likely to participate. Dynamical simulation of CID experiments of Py2+ for different collision energies between 2.5 and 30 eV is also presented. The dynamical simulations allow to understand the dissociation processes. The agreement between the simulated and measured mass spectra suggests that the main processes are captured by this approach. It appears that most of the dissociation occurs on a short timescale (less than 3 ps). Analysis of the kinetic energy partition is used to get insights into the collision/dissociation processes at the atomic scale. The simulated mass spectra of the parent and dissociated products are obtained from the combination of molecular dynamics simulations and phase space theory to address the short and long timescales dissociation, respectively

Generating Text Sequence Images for Recognition

Recently, methods based on deep learning have dominated the field of text recognition. With a large number of training data, most of them can achieve the state-of-the-art performances. However, it is hard to harvest and label sufficient text sequence images from the real scenes. To mitigate this issue, several methods to synthesize text sequence images were proposed, yet they usually need complicated preceding or follow-up steps. In this work, we present a method which is able to generate infinite training data without any auxiliary pre/post-process. We tackle the generation task as an image-to-image translation one and utilize conditional adversarial networks to produce realistic text sequence images in the light of the semantic ones. Some evaluation metrics are involved to assess our method and the results demonstrate that the caliber of the data is satisfactory. The code and dataset will be publicly available soon

Transferencia tecnológica y desarrollo sostenible = Technology transfer and sustainable development

En este trabajo comienza con una aproximación al estudio del cambio climático y sus impactos económicos, para analizar seguidamente el marco delimitado por la Convención Marco de Naciones Unidas sobre el Cambio Climático, el Protocolo de Kioto y el Acuerdo de París. Posteriormente la investigación se dirige hacia la transferencia tecnológica, mediante la utilización del Mecanismo de Desarrollo Limpio (MDL), en China e India, los dos mayores países del mundo por número de habitantes, a fin de comprobar cómo actúa este instrumento para alcanzar un desarrollo limpio ante estrategias políticas y económicas diferentes. El MDL, diseñado en el Protocolo de Kioto, ha estimulado el registro de miles de proyectos climáticos y de desarrollo en todo el mundo. La experiencia acumulada puede inspirar, informar y prestar infraestructura para el diseño y la puesta en práctica de las herramientas económicas que, bajo el Acuerdo de París, facilitan la transferencia tecnológica para reducir o absorber las emisiones de gases de efecto invernadero (GEI), incrementar la capacidad de adaptación y la resiliencia ante el cambio climático y, a la vez, promover un desarrollo sostenible. A ello se destina la última parte de esta investigación

Distributions of aluminum, manganese, cobalt, and lead in the western South Pacific: Interplay between the South and North Pacific

Aluminum (Al), manganese (Mn), cobalt (Co), and lead (Pb) are strongly scavenged from seawater. We reported that each element is uniquely related to ocean circulation in the North Pacific (Zheng et al., 2019). Herein, we present the full-depth distributions of these elements in the western South Pacific, which include meridional sections along 170°W (GEOTRACES GP19). We determined dissolved (d) and total dissolvable (td) concentrations using filtered and unfiltered seawater without UV treatment, and we calculated labile particulate (lp) concentrations as the difference between td and d concentrations. This and the previous studies present the basin scale distributions, which enable us to investigate first order processes that drive the biogeochemistry of Al, Mn, Co, and Pb in the Pacific Ocean. The meridional section of dAl along 170°W (GP19)-160°W (GPc06) from 64°S to 54°N indicates that elevated concentrations (maximum 6.1 nmol/kg) occur between 40°S and 10°S from surface to bottom. However, the maxima of lpAl occur at high latitudes. The lpAl/tdAl ratio has a minimum of 0.26 ± 0.12 (ave ± sd, n = 116) in the zone from 30°S to 0°S. Based on these results, we propose a hypothesis that weathering on land has a significant effect on the distribution of Al in the ocean. Intensive weathering on tropical and subtropical islands and Australia forms kaolinite-dominated soils and laterite. This process provides dAl and kaolinite to the ocean. The supply of kaolinite results in kaolinite-dominated sediments that become a major bottom source for dAl. In contrast, strong sources of Mn and Co are continental shelves around the northern boundary. Dissolved Mn and dCo are released from sediments by manganese reduction and carried by intermediate water circulation. In particular, dCo spreads in the North Pacific Intermediate Water (NPIW), Equatorial Pacific Intermediate Water (EqPIW), and Antarctic Intermediate Water (AAIW); 23–59 pmol/kg at a potential density anomaly (σθ) of 27.0. This is partly owing to the uptake of dCo by phytoplankton and remineralization from settling particles. The dPb concentrations are 10 ± 6 pmol/kg (n = 397) in the South Pacific and 30 ± 20 pmol/kg (n = 566) in the North Pacific. The distribution of dPb is characterized by a maximum in the Subtropical Mode Water (SMW) and Central Mode Water (CMW) with σθ∼26 in the North Pacific. These results indicate that Pb is predominantly supplied by anthropogenic aerosols from Asia and Russia to the Pacific Ocean. Because Pb is not actively taken up by phytoplankton, Pb enters mode waters during winter convection and is transported with mode waters

Solid-phase extraction of palladium, platinum, and gold from water samples: comparison between a chelating resin and a chelating fiber with ethylenediamine groups

Dissolved palladium (Pd), platinum (Pt), and gold (Au) form inert chloride complexes at low concentrations of pmol/kg in environmental water, thus rendering difficulty in the development of a precise analytical method for these metals. Herein, we report the preconcentration of Pd, Pt, and Au with a chelating fiber Vonnel-en and a chelating resin TYP-en with ethylenediamine (en) groups. Batch adsorption experiments reveal the adsorption capacity of Vonnel-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl as 0.53, 0.22, and 0.27 mmol/g, respectively. The adsorption capacity of TYP-en for Pd(II), Pt(IV), and Au(III) in 0.10 M HCl is 0.31, 0.17, and 0.52 mmol/g, respectively. In column extraction experiments using small-volume samples containing Pd(II), Pt(II), Pt(IV), Au(I), or Au(III) at concentrations of μmol/kg, TYP-en is able to quantitatively recover Pd, Pt, and Au from 0.01 to 0.2 M HCl irrespective of their oxidation states. In contrast, Vonnel-en is unable to quantitatively recover Au(I). In column extraction experiments using large-volume samples containing Pd(II), Pt(IV), and Au(III) at concentrations of pmol/kg, the recovery of Pd(II), Pt(IV), and Au(III) by TYP-en from 0.07 M HCl is 100–105%. However, the recovery of Pd(II), Pt(IV), and Au(III) by Vonnel-en from 0.03 to 0.3 M HCl is 102–110, 7–15, and 20–52%, respectively. Thus, the chelating resin TYP-en has a high potential for the multielemental determination of Pd, Pt, and Au in environmental water

Sectional Distribution Patterns of Cd, Ni, Zn, and Cu in the North Pacific Ocean: Relationships to Nutrients and Importance of Scavenging

The North Pacific Ocean is located at the end of the thermohaline circulation of deep water. This study reports on basin-scale full-depth sectional distributions of total dissolvable (td), dissolved (d), and labile particulate (lp) Cd, Ni, Zn, and Cu along three transects: the GEOTRACES transects GP18 (165°E) and GP02 (47°N), and along 160°W. We find that scavenging is an important factor that significantly affects the distributions of dZn, dNi, and dCu, of which the magnitude of influence increases in the order of Cd 800 m deep, which is in the range of the phytoplankton Cd/P ratio. This is indicative of the dominant effect of water circulation and biological processes on dCd distribution. The dissolved metals (dMs) to PO₄ ratios of other examined metals were either partially or completely outside the range of typical biomass ratios. They generally increased with depth in waters >800 m deep; the magnitude of increase was the highest for Cu and moderate for Ni and Zn. Below 800 m, an increase in the apparent oxygen utilization from 150 to 300 μmol/kg was concurrent with a decrease in the dMs/PO4 ratios: 4 ± 3% for Cd, 21 ± 4% for Zn, 21 ± 3% for Ni, and 69 ± 7% for Cu

Distribution and stoichiometry of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in the East China Sea

The dissolved (d) and total dissolvable (td) trace metals were determined in seawater samples collected from the East China Sea (ECS). Labile particulate (lp) species was calculated as td minus d, and the sectional and vertical distributions of d and lp trace metals were evaluated. The surface concentrations of dAl, dCo, dNi, dCu, and dPb were higher in the continental shelf region than in the Kuroshio region. lpAl and lpFe were the dominant species below a depth of 400 m, and a strong positive correlation was observed between them in the Kuroshio region. The enrichment factor (EF) against crustal abundance was calculated for the purpose of estimating the origin of dMs in the ECS. The EF(dFe) was close to unity. These results suggest that both lpFe and dFe are dominated by crustal sources. The other elements had high EF, indicating significant contributions from other sources. EF(dPb) was close to the enrichment factor in aerosol, suggesting atmospheric input from anthropogenic sources. The dM/P ratios were calculated to investigate the validity of the extended Redfield ratio in the ECS. The Mn/P, Co/P, Cu/P, Zn/P, and Cd/P ratios in shallow water (< 200 m) were within the same order of magnitude as those in phytoplankton. In contrast, the Al/P and Fe/P ratios were, respectively, 27 and 213 times higher in phytoplankton compared to those in shallow water. These results suggest that dFe is a potential limiting factor for biological production, although it is not exhausted in surface water