Synthesis, luminescence, energy transfer and Langmuir-Blodgett films of amphiphilic complexes of rare earths with monooctadecyl phthalate

Three new amphiphilic rare earth complexes with only two organic long chains Ln (MOP)(2)Cl (MOP=monooctadecyl phthalate, Ln=Eu, Tb, Gd) were synthesized and characterized by elemental analysis. The complexes (Eu, Tb) showed good luminescence property with long fluorescence lifetime, whereas the intensity and lifetime of Tb complex are greater than those of Eu complex, By measuring the triplet energy levels of ligand based on energy transfer mechanism, above phenomena have been well explained. The Langmuir films of the complexes on the air/water interface were also studied and the results show that all of them have good film-forming property.

LIFETIME MEASUREMENTS OF SOME TMI ODD PARITY LEVELS

Eleven new lifetimes of odd parity excited energy levels in four configurations: 4f12 5d 6s 6p, 4f12 6S2 6p, 4f13 5d 6s and 4f13 6s 7s of atomic thulium have been mesured with atomic-beam laser spectrocopy. Two pulsed dye lasers are used for stepwise excitation and the time-resolved fluorescence decay was used to determine lifetime values. The accuracy of the measurements is about 10%.

The effect of some triazole derivatives as inhibitors for the corrosion of mild steel in 1 M hydrochloric acid

Corrosion inhibition by some new triazole derivatives on mild steel in 1 M hydrochloric acid solutions has been investigated by weight loss test, electrochemical measurement, scanning electronic microscope analysis and quantum chemical calculations. The results indicate that these compounds act as mixed-type inhibitors retarding the anodic and cathodic corrosion reactions and do not change the mechanism of either hydrogen evolution reaction or mild steel dissolution. The studied compounds following the Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The effect of molecular structure on the inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as highest occupied molecular orbital (HOMO), lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were calculated. (C) 2009 Published by Elsevier B.V.

Experimental and theoretical investigation of the adsorption behaviour of new triazole derivatives as inhibitors for mild steel corrosion in acid media

Three triazole derivatives (4-chloro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (CATM), 4-methoxyl-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (MATM) and 4-fluoro-acetophenone-O-1'-(1',3',4'-triazolyl)-metheneoxime (FATM)) have been synthesized as new inhibitors for the corrosion of mild steel in acid media. The inhibition efficiencies of these inhibitors were evaluated by means of weight loss and electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and polarization curves. Then the surface morphology was studied by scanning electron microscopy (SEM). The adsorption of triazole derivatives is found to obey Langmuir adsorption isotherm, and the thermodynamic parameters were determined and discussed. The relationship between molecular structure of these compounds and their inhibition efficiency has been investigated by ab initio quantum chemical calculations. The electronic properties such as the highest occupied molecular orbital (HOMO), the lowest unoccupied molecular orbital (LUMO) energy levels, energy gap (LUMO-HOMO), dipole moment and molecular orbital densities were computed. (c) 2007 Elsevier Ltd. All rights reserved.

Correlations in low dimensional quantum systems

In this thesis I present the work done during my PhD in the area of low dimensional quantum gases. The chapters of this thesis are self contained and represent individual projects which have been peer reviewed and accepted for publication in respected international journals. Various systems are considered, the first of which is a two particle model which possesses an exact analytical solution. I investigate the non-classical correlations that exist between the particles as a function of the tunable properties of the system. In the second work I consider the coherences and out of equilibrium dynamics of a one-dimensional Tonks-Girardeau gas. I show how the coherence of the gas can be inferred from various properties of the reduced state and how this may be observed in experiments. I then present a model which can be used to probe a one-dimensional Fermi gas by performing a measurement on an impurity which interacts with the gas. I show how this system can be used to observe the so-called orthogonality catastrophe using modern interferometry techniques. In the next chapter I present a simple scheme to create superposition states of particles with special emphasis on the NOON state. I explore the effect of inter-particle interactions in the process and then characterise the usefulness of these states for interferometry. Finally I present my contribution to a project on long distance entanglement generation in ion chains. I show how carefully tuning the environment can create decoherence-free subspaces which allows one to create and preserve entanglement.

Techniques for engineering quantum states

In this thesis I theoretically study quantum states of ultracold atoms. The majority of the Chapters focus on engineering specific quantum states of single atoms with high fidelity in experimentally realistic systems. In the sixth Chapter, I investigate the stability and dynamics of new multidimensional solitonic states that can be created in inhomogeneous atomic Bose-Einstein condensates. In Chapter three I present two papers in which I demonstrate how the coherent tunnelling by adiabatic passage (CTAP) process can be implemented in an experimentally realistic atom chip system, to coherently transfer the centre-of-mass of a single atom between two spatially distinct magnetic waveguides. In these works I also utilise GPU (Graphics Processing Unit) computing which offers a significant performance increase in the numerical simulation of the Schrödinger equation. In Chapter four I investigate the CTAP process for a linear arrangement of radio frequency traps where the centre-of-mass of both, single atoms and clouds of interacting atoms, can be coherently controlled. In Chapter five I present a theoretical study of adiabatic radio frequency potentials where I use Floquet theory to more accurately model situations where frequencies are close and/or field amplitudes are large. I also show how one can create highly versatile 2D adiabatic radio frequency potentials using multiple radio frequency fields with arbitrary field orientation and demonstrate their utility by simulating the creation of ring vortex solitons. In the sixth Chapter I discuss the stability and dynamics of a family of multidimensional solitonic states created in harmonically confined Bose-Einstein condensates. I demonstrate that these solitonic states have interesting dynamical instabilities, where a continuous collapse and revival of the initial state occurs. Through Bogoliubov analysis, I determine the modes responsible for the observed instabilities of each solitonic state and also extract information related to the time at which instability can be observed.

Finite size effects in the presence of a chemical potential: A study in the classical nonlinear O(2) sigma model

In the presence of a chemical potential, the physics of level crossings leads to singularities at zero temperature, even when the spatial volume is finite. These singularities are smoothed out at a finite temperature but leave behind nontrivial finite size effects which must be understood in order to extract thermodynamic quantities using Monte Carlo methods, particularly close to critical points. We illustrate some of these issues using the classical nonlinear O(2) sigma model with a coupling β and chemical potential μ on a 2+1-dimensional Euclidean lattice. In the conventional formulation this model suffers from a sign problem at nonzero chemical potential and hence cannot be studied with the Wolff cluster algorithm. However, when formulated in terms of the worldline of particles, the sign problem is absent, and the model can be studied efficiently with the "worm algorithm." Using this method we study the finite size effects that arise due to the chemical potential and develop an effective quantum mechanical approach to capture the effects. As a side result we obtain energy levels of up to four particles as a function of the box size and uncover a part of the phase diagram in the (β,μ) plane. © 2010 The American Physical Society.

Strong configuration mixing among the fine-structure levels of Cl+

A large-scale configuration interaction (Cl) calculation using Program CIV3 of Hibbert is performed for the lowest 62 fine- structure levels of the singly charged chlorine ion. Our calculated energy levels agree very well with most of the NIST results and confirm the identification of the lowest P-1(o) as actually 3s(2)3p(3)(D-2(o))3d P-1(o) rather than the generally employed 3s3p(5) P-1(o) in measurements and calculations. Discrepancies in the energy positions of some symmetries are found and discussed. Some large oscillator strengths for allowed and intercombination transitions in both length and velocity gauges are presented. Their close agreement gives credence to the accuracy of our CI wavefunctions.

Plane wave and Coulomb asymptotics

A simple plane wave solution of the Schrodinger-Helmholtz equation is a quantum eigenfunction obeying both energy and linear momentum correspondence principles. Inclusion of the outgoing wave with scattering amplitude f asymptotic development of the plane wave, we show that there is a problem with angular momentum when we consider forward scattering at the point of closest approach and at large impact parameter given semiclassically by (l + 1/2)/k where l is the azimuthal quantum number and may be large (J. Leech et al., Phys. Rev. Lett. 88. 257901 (2002)). The problem is resolved via non- uniform, non-standard analysis involving the Heaviside step function, unifying classical, semiclassical and quantum mechanics, and the treatment is extended to the case of pure Coulomb scattering.

Classical computation with quantum systems

As semiconductor electronic devices scale to the nanometer range and quantum structures (molecules, fullerenes, quantum dots, nanotubes) are investigated for use in information processing and storage, it, becomes useful to explore the limits imposed by quantum mechanics on classical computing. To formulate the problem of a quantum mechanical description of classical computing, electronic device and logic gates are described as quantum sub-systems with inputs treated as boundary conditions, outputs expressed.is operator expectation values, and transfer characteristics and logic operations expressed through the sub-system Hamiltonian. with constraints appropriate to the boundary conditions. This approach, naturally, leads to a description of the subsystem.,, in terms of density matrices. Application of the maximum entropy principle subject to the boundary conditions (inputs) allows for the determination of the density matrix (logic operation), and for calculation of expectation values of operators over a finite region (outputs). The method allows for in analysis of the static properties of quantum sub-systems.

Probing quantum communication rules by addition and subtraction of single photons to/from a light field

The possibility of arbitrarily "adding" and "subtracting" single photons to and from a light field may give access to a complete engineering of quantum states and to fundamental quantum phenomena. We experimentally implemented simple alternated sequences of photon creation and annihilation on a thermal field and used quantum tomography to verify the peculiar character of the resulting light states. In particular, as the final states depend on the order in which the two actions are performed, we directly observed the noncommutativity of the creation and annihilation operators, one of the cardinal concepts of quantum mechanics, at the basis of the quantum behavior of light. These results represent a step toward the full quantum control of a field and may provide new resources for quantum information protocols

Magnetic properties of copper hexadecaphthalocyanine (F16CuPc) thin films and powders

The structural and magnetic properties of F16CuPc thin films and powder, including x-ray diffraction (XRD), superconducting quantum interference device (SQUID) magnetometry, and theoretical modelling of exchange interactions are reported. Analysis of XRD from films, with thickness ranging between 100 and 160 nm, deposited onto Kapton and a perylene-3,4,9,10-tetracarboxylic-3,4,9,10-dianhydride (PTCDA) interlayer shows that the stacking angle (defined in the text) of the film is independent of the thickness, but that the texture is modified by both film thickness and substrate chemistry. The SQUID measurements suggest that all samples are paramagnetic, a result that is confirmed by our theoretical modelling including density functional theory calculations of one-dimensional molecular chains and Green's function perturbation theory calculations for a molecular dimer. By investigating theoretically a range of different geometries, we predict that the maximum possible exchange interaction between F16CuPc molecules is twice as large as that in unfluorinated copper-phthalocyanine (CuPc). This difference arises from the smaller intermolecular spacing in F16CuPc. Our density functional theory calculation for isolated F16CuPc molecule also shows that the energy levels of Kohn-Sham orbitals are rigidly shifted similar to 1 eV lower in F16CuPc compared to CuPc without a significant modification of the intramolecular spin physics, and that therefore the two molecules provide a suitable platform for independently varying magnetism and charge transport. 

Tests of multimode quantum nonlocality with homodyne measurements

We investigate the violation of local realism in Bell tests involving homodyne measurements performed on multimode continuous-variable states. By binning the measurement outcomes in an appropriate way, we prove that the Mermin-Klyshko inequality can be violated by an amount that grows exponentially with the number of modes. Furthermore, the maximum violation allowed by quantum mechanics can be attained for any number of modes, albeit requiring a quantum state whose generation is hardly practicable. Interestingly, this exponential increase of the violation holds true even for simpler states, such as multipartite GHZ states. The resulting benefit of using more modes is shown to be significant in practical multipartite Bell tests by analyzing the increase of the robustness to noise with the number of modes. In view of the high efficiency achievable with homodyne detection, our results thus open a possible way to feasible loophole-free Bell tests that are robust to experimental imperfections. We provide an explicit example of a three-mode state (a superposition of coherent states) which results in a significantly high violation of the Mermin-Klyshko inequality (around 10%) with homodyne measurements.

Universal tight binding model for chemical reactions in solution and at surfaces. II. Water

A revised water model intended for use in condensed phase simulations in the framework of the self consistent polarizable ion tight binding theory is constructed. The model is applied to water monomer, dimer, hexamers, ice, and liquid, where it demonstrates good agreement with theoretical results obtained by more accurate methods, such as DFT and CCSD(T), and with experiment. In particular, the temperature dependence of the self diffusion coefficient in liquid water predicted by the model, closely reproduces experimental curves in the temperature interval between 230 K and 350 K. In addition, and in contrast to standard DFT, the model properly orders the relative densities of liquid water and ice. A notable, but inevitable, shortcoming of the model is underestimation of the static dielectric constant by a factor of two. We demonstrate that the description of inter and intramolecular forces embodied in the tight binding approximation in quantum mechanics leads to a number of valuable insights which can be missing from ab initio quantum chemistry and classical force fields. These include a discussion of the origin of the enhanced molecular electric dipole moment in the condensed phases, and a detailed explanation for the increase of coordination number in liquid water as a function of temperature and compared with ice-leading to insights into the anomalous expansion on freezing. The theory holds out the prospect of an understanding of the currently unexplained density maximum of water near the freezing point. 

Formation mechanism of levoglucosan and formaldehyde during cellulose pyrolysis

Biomass pyrolysis is an efficient way to transform raw biomass or organic waste materials into useable energy, including liquid, solid, and gaseous materials. Levoglucosan (1,6-anhydro-β-d-glucopyranose) and formaldehyde are two important products in biomass pyrolysis. The formation mechanism of these two products was investigated using the density functional theory (DFT) method based on quantum mechanics. It was found that active anhydroglucose can be obtained from a cellulose homolytic reaction during high-temperature steam gasification of the biomass process. Anhydroglucose undergoes a hydrogen-donor reaction and forms an intermediate, which can transform into the products via three pathways, one (path 1) for the formation of levoglucosan and two (paths 2 and 3) for formaldehyde. A total of six elementary reactions are involved. At a pressure of 1 atm, levoglucosan can be formed at all of the temperatures (450-750 K) considered in this simulation, whereas formaldehyde can be formed only when the temperature is higher than 475 K. Moreover, the energy barrier of levoglucosan formation is lower than that of formaldehyde, which is in agreement with the mechanism proposed in the experiments. © 2011 American Chemical Society.