Carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium

We theoretically investigate carrier-envelope phase dependence of few-cycle ultrashort laser pulse propagation in a polar molecule medium. Our results show that a soliton pulse can be generated during the two-photon resonant propagation of few-cycle pulse in the polar molecule medium. Moreover, the main features of the soliton pulse, such as pulse duration and intensity, depend crucially on the carrier-envelope phase of the incident pulse, which could be utilized to determine the carrier-envelope phase of a few-cycle ultrashort laser pulse from a mode-locked oscillator.

Phytoplankton periodicity: its motivation, mechanisms and manipulation

This review summarizes some recent work to find a generalized explanation of phytoplankton periodicity in lakes. Much of the observational and experimental evidence is drawn from work centred on the large enclosures (Lund Tubes) installed in Blelham Tarn, English Lake District. Observations on the phytoplankton in the tubes are related to the periodic changes that occur in natural lakes and it is suggested that such changes have common patterns, that they are due to common causes, that they are affected by similar processes and that they are therefore predictable and, potentially, manipulable.

Part I. Approximate Hartree-Fock wavefunctions one-electron properties and electronic structure of the water molecule. Part II. Perturbation-variational calculation of the nuclear spin-spin isotope coupling constant in HD

Part I

Several approximate Hartree-Fock SCF wavefunctions for the ground electronic state of the water molecule have been obtained using an increasing number of multicenter s, p, and d Slater-type atomic orbitals as basis sets. The predicted charge distribution has been extensively tested at each stage by calculating the electric dipole moment, molecular quadrupole moment, diamagnetic shielding, Hellmann-Feynman forces, and electric field gradients at both the hydrogen and the oxygen nuclei. It was found that a carefully optimized minimal basis set suffices to describe the electronic charge distribution adequately except in the vicinity of the oxygen nucleus. Our calculations indicate, for example, that the correct prediction of the field gradient at this nucleus requires a more flexible linear combination of p-orbitals centered on this nucleus than that in the minimal basis set. Theoretical values for the molecular octopole moment components are also reported.

Part II

The perturbation-variational theory of R. M. Pitzer for nuclear spin-spin coupling constants is applied to the HD molecule. The zero-order molecular orbital is described in terms of a single 1s Slater-type basis function centered on each nucleus. The first-order molecular orbital is expressed in terms of these two functions plus one singular basis function each of the types e^-r/r and e^-r ln r centered on one of the nuclei. The new kinds of molecular integrals were evaluated to high accuracy using numerical and analytical means. The value of the HD spin-spin coupling constant calculated with this near-minimal set of basis functions is J_HD = +96.6 cps. This represents an improvement over the previous calculated value of +120 cps obtained without using the logarithmic basis function but is still considerably off in magnitude compared with the experimental measurement of J_HD = +43 0 ± 0.5 cps.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

Fear and manipulation in George Orwells Nineteen Eighty-Four and Alan Moores V for Vendetta

O objetivo desta dissertação é analisar a questão da política do medo e das várias formas de manipulação da realidade encontradas nas narrativa de 1984 (1949), de George Orwell, assim como na narrativa gráfica de V de Vingança tanto na sua versão em quadrinhos, de Alan Moore (1982-88), quanto na sua adaptação cinematográfica, escrita pelos Wachowskis (2005). Em particular, tenta demonstrar similaridades nas técnicas usadas, assim como na análise dos personagens, procurando embasar certos questionamentos com a ajuda de filósofos políticos, estudos de psicologia, culturais, e distópicos. Ao final, este trabalho tenta identificar a importância da influência dos autores estudados, assim como outros autores distópicos, na criação e desenvolvimento de uma nova geração social de mentalidade inconformista

Multiple grasp-specific representations of tool dynamics mediate skillful manipulation.

Skillful tool use requires knowledge of the dynamic properties of tools in order to specify the mapping between applied force and tool motion. Importantly, this mapping depends on the orientation of the tool in the hand. Here we investigate the representation of dynamics during skillful manipulation of a tool that can be grasped at different orientations. We ask whether the motor system uses a single general representation of dynamics for all grasp contexts or whether it uses multiple grasp-specific representations. Using a novel robotic interface, subjects rotated a virtual tool whose orientation relative to the hand could be varied. Subjects could immediately anticipate the force direction for each orientation of the tool based on its visual geometry, and, with experience, they learned to parameterize the force magnitude. Surprisingly, this parameterization of force magnitude showed limited generalization when the orientation of the tool changed. Had subjects parameterized a single general representation, full generalization would be expected. Thus, our results suggest that object dynamics are captured by multiple representations, each of which encodes the mapping associated with a specific grasp context. We suggest that the concept of grasp-specific representations may provide a unifying framework for interpreting previous results related to dynamics learning.