Effects of rotation in the laser-pulse photoassociation in a thermal gas of atoms

Photoassociation is a possible route for the formation of chemical bonds. In this process, the binding of colliding atoms can be induced by means of a laser field. Photoassociation has been studied in the ultracold regime and also with temperatures well above millikelvins in the thermal energy domain, which is a situation commonly encountered in the laboratory. A photoassociation mechanism can be envisioned based on the use of infrared pulses to drive a transition from free colliding atoms on the electronic ground state to form a molecule directly on that state. This work takes a step in this direction, investigating the laser-pulse-driven formation of heteronuclear diatomic molecules in a thermal gas of atoms including rotational effects. Based on the assumption of full system controllability, the maximum possible photoassociation yield is deduced. The photoassociation probability is calculated as a function of the laser parameters for different temperatures. Additionally, the photoassociation yield induced by subpicosecond pulses of a priori fixed shape is compared to the maximum possible yield.

Single-Particle Momentum Distributions for Bosonic Trimer States in Two and Three Dimensions

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Reversibility of Thermal Transitions in Dilute Dioctadecyl-Dimethyl-Ammonium Bromide Vesicles

Dioctadecyl-dimethyl-ammonium bromide (DODAB) vesicles can be characterized by their differential scanning calorimetry (DSC) thermograms comprised of two endotherms at T (s) a parts per thousand 36 A degrees C and T (m) a parts per thousand 45 A degrees C in the heating, ascribed respectively to the subgel-to-gel and gel-to-liquid crystalline transitions, and two exotherms at T'(m) a parts per thousand 40 A degrees C and T'(s) a parts per thousand 16 A degrees C in the cooling, ascribed respectively to the liquid crystalline-to-gel and gel-to-subgel transitions. It has been reported but not proved that the T (m)-transitions, the T'(m)-transitions, the T (s)-transitions, and the T'(s)-transitions are reverse to each other, displaying hystheresis Delta T (m) a parts per thousand 5 A degrees C and Delta T (s) a parts per thousand 20-25 A degrees C, respectively. By investigating the effects of the initial scanning temperature (T (i)) on the transition enthalpies (Delta H (m), Delta H (s), Delta H'(m) and Delta H'(s)), we have seen that these transitions are the reverse to each other and display different kinetics.

Radiative association of Ti and O atoms

Rate coefficients for the radiative association of titanium and oxygen atoms to form the titanium monoxide (TiO) molecule are estimated. The radiative association of Ti(F-3) and O(P-3) atoms is dominated by an approach along the C-3 Delta potential energy curve, accompanied by spontaneous emission into the X-3 Delta ground state of TiO. For temperatures ranging from 300-14 000 K, the total rate coefficients are found to vary from 4.76 x 10(-17) to 9.96 x 10(-17) cm(3) s(-1), respectively.

Electrostatic potentials and polarization effects in proton-molecule interactions by means of multipoles from the quantum theory of atoms in molecules

Some atomic multipoles (charges, dipoles and quadrupoles) from the Quantum Theory of Atoms in Molecules (QTAIM) and CHELPG charges are used to investigate interactions between a proton and a molecule (F2, Cl2, BF, AlF, BeO, MgO, LiH, H2CO, NH3, PH3, BF3, and CO2). Calculations were done at the B3LYP/6-311G(3d,3p) level. The main aspect of this work is the investigation of polarization effects over electrostatic potentials and atomic multipoles along a medium to long range of interaction distances. Large electronic charge fluxes and polarization changes are induced by a proton mainly when this positive particle approaches the least electronegative atom of diatomic heteronuclear molecules. The search for simple equations to describe polarization on electrostatic potentials from QTAIM quantities resulted in linear relations with r-4 (r is the interaction distance) for many cases. Moreover, the contribution from atomic dipoles to these potentials is usually the most affected contribution by polarization what reinforces the need for these dipoles to a minimal description of purely electrostatic interactions. Finally, CHELPG charges provide a description of polarization effects on electrostatic potentials that is in disagreement with physical arguments for certain of these molecules. (c) 2012 Wiley Periodicals, Inc.

Dilute Acid Hydrolysis of Sugar Cane Bagasse at High Temperatures: A Kinetic Study of Cellulose Saccharification and Glucose Decomposition. Part I: Sulfuric Acid as the Catalyst

The kinetics of sugar cane bagasse cellulose saccharification and the decomposition of glucose under extremely low acid (ELA) conditions, (0.07%), 0.14%, and 0.28% H2SO4, and at high temperatures were investigated using batch reactors. The first-order rate constants were obtained by weight loss, remaining glucose, and fitting glucose concentration profiles determined with HPLC using the Saeman model. The maximum glucose yields reached 67.6% (200 degrees C, 0.07% H2SO4, 30 min), 69.8% (210 degrees C, 0.14% H2SO4, 10 min), and 67.3% (210 degrees C, 0.28% H2SO4, 6 min). ELA conditions produced remarkable glucose yields when applied to bagasse cellulose. The first-order rate constants were used to calculate activation energies and extrathermodynamic parameters to elucidate the reaction mechanism under ELA conditions. The effect of acid concentration on cellulose hydrolysis and glucose decomposition was also investigated. The observed activation energies and reaction orders with respect to hydronium ion for cellulose hydrolysis and glucose decomposition were 184.9 and 124.5 kJ/mol and 1.27 and 0.75, respectively.

Structural properties and energetics of diffuse Rb-87 clusters in three-dimension

A correlated two-body basis function is used to describe the three-dimensional bosonic clusters interacting via two-body van der Waals potential. We calculate the ground state and the zero orbital angular momentum excited states for Rb-N clusters with up to N = 40. We solve the many-particle Schrodinger equation by potential harmonics expansion method, which keeps all possible two-body correlations in the calculation and determines the lowest effective many-body potential. We study energetics and structural properties for such diffuse clusters both at dimer and tuned scattering length. The motivation of the present study is to investigate the possibility of formation of N-body clusters interacting through the van der Waals interaction. We also compare the system with the well studied He, Ne, and Ar clusters. We also calculate correlation properties and observe the generalised Tjon line for large cluster. We test the validity of the shape-independent potential in the calculation of the ground state energy of such diffuse cluster. These are the first such calculations reported for Rb clusters. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4730972]

Optical parametric oscillation with distributed feedback in cold atoms

There is currently a strong interest in mirrorless lasing systems(1), in which the electromagnetic feedback is provided either by disorder (multiple scattering in the gain medium) or by order (multiple Bragg reflection). These mechanisms correspond, respectively, to random lasers(2) and photonic crystal lasers(3). The crossover regime between order and disorder, or correlated disorder, has also been investigated with some success(4-6). Here, we report one-dimensional photonic-crystal lasing (that is, distributed feedback lasing(7,8)) with a cold atom cloud that simultaneously provides both gain and feedback. The atoms are trapped in a one-dimensional lattice, producing a density modulation that creates a strong Bragg reflection with a small angle of incidence. Pumping the atoms with auxiliary beams induces four-wave mixing, which provides parametric gain. The combination of both ingredients generates a mirrorless parametric oscillation with a conical output emission, the apex angle of which is tunable with the lattice periodicity.

Two-Photon Cooperative Absorption in Colliding Cold Na Atoms

Two-photon cooperative absorption is common in solid-state physics. In a sample of trapped cold atoms, this effect may open up new possibilities for the study of nonlinear effects. The experiment described herein starts with two colliding Na atoms in the S hyperfine ground state. The pair absorb two photons, resulting in both a P-1/2 and a P-3/2 atom. This excitation is observed by ionization using an external light source. A simple model that considers only dipole-dipole interactions between the atoms allows us to understand the basic features observed in the experimental results. Both the pair of generated atoms and the photons originating from their decay are correlated and may have interesting applications that remain to be explored.

Calculations of the spectral shifts and line profiles of alkaline earth atoms in liquid helium environment

Liquid configurations generated by Metropolis Monte Carlo simulations are used in time-dependent density functional theory calculations of the spectral line shifts and line profiles of the lowest lying excitation of the alkaline earth atoms, Be, Mg, Ca, Sr and Ba embedded in liquid helium. The results are in very good agreement with the available experimental data. Special attention is given to the calculated spectroscopic shift and the associated line broadening. The analysis specifies the inhomogeneous broadening of the three separate contributions due to the splitting of the s -> p transition of the alkaline earth atom in the liquid environment. (C) 2012 Elsevier B. V. All rights reserved.

Source of slow lithium atoms from Ne or H-2 matrix isolation sublimation

We have studied, via laser absorption spectroscopy, the velocity distribution of Li-7 atoms released from cryogenic matrices of solid neon or molecular hydrogen. The Li atoms are implanted into the Ne or H-2 matrices - grown onto a sapphire substrate - by laser ablation of a solid Li or LiH precursor. A heat pulse is then applied to the sapphire substrate sublimating the matrix together with the isolated atoms. With a NiCr film resistor deposited directly onto the sapphire substrate we are able to transfer high instantaneous power to the matrix, thus reaching a fast sublimation regime. In this regime the Li atoms can get entrained in the released matrix gas, and we were also able to achieve matrix sublimation times down to 10 mu s for both H-2 or Ne matrix, enabling us to proceed with the trapping of the species of our interest such as atomic hydrogen, lithium, and molecules. The sublimation of the H-2 matrix, with its large center-of-mass velocity, provides evidence for a new regime of one-dimensional thermalization. The laser ablated Li seems to penetrate the H-2 matrix deeper than it does in Ne. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4704125]

Liquid crystalline oligofluorenes and their derivatives

Homo-oligofluorenes (OFn), polyfluorenes (PF2/6) and oligofluorenes with one fluorenenone group in the center (OFnK) were synthesized. They were used as model compounds to understand of the structure-property relationships of polyfluorenes and the origin of the green emission in the photoluminescence (after photooxidation of the PFs) and the electroluminescence (EL) spectra. The electronic, electrochemical properties, thermal behavior, supramolecular self-assembly, and photophysical properties of OFn, PF2/6 and OFnK were investigated. Oligofluorenes with 2-ethylhexyl side chain (OF2-OF7) from the dimer up to the heptamer were prepared by a series of stepwise transition metal mediated Suzuki and Yamamoto coupling reactions. Polyfluorene was synthesized by Yamamoto coupling of 2,7-dibromo-9,9-bis(2-ethylhexyl)fluorene. Oligofluorenes with one fluorenone group in the center (OF3K, OF5K, OF7K) were prepared by Suzuki coupling between the monoboronic fluorenyl monomer, dimer, trimer and 2, 7-dibromofluorenone. The electrochemical and electronic properties of homo-oligofluorenes (OFn) were systematically studied by several combined techniques such as cyclic voltammetry, differential pulse voltammetry, UV-vis absorption spectroscopy, steady and time-resolved fluorescence spectroscopy. It was found that the oligofluorenes behave like classical conjugated oligomers, i.e., with the increase of the chain-length, the corresponding oxidation potential, the absorption and emission maximum, ionization potential, electron affinity, band gap and the photoluminescence lifetime displayed a very good linear relation with the reciprocal number of the fluorene units (1/n). The extrapolation of these linear relations to infinite chain length predicted the electrochemical and electronic properties of the corresponding polyfluorenes. The thermal behavior, single-crystal structure and supramolecular packing, alignment properties, and molecular dynamics of the homo-oligofluorenes (OFn) up to the polymer were studied using techniques such as TGA, DSC, WAXS, POM and DS. The OFn from tetramer to heptamer show a smectic liquid crystalline phase with clearly defined isotropization temperature. The oligomers do show a glass transition which exhibits n-1 dependence and allows extrapolation to a hypothetical glass transition of the polymer at around 64 °C. A smectic packing and helix-like conformation for the oligofluorenes from tetramer to heptamer was supported by WAXS experiments, simulation, and single-crystal structure of some oligofluorene derivatives. Oligofluorenes were aligned more easily than the corresponding polymer, and the alignability increased with the molecular length from tetramer to heptamer. The molecular dynamics in a series of oligofluorenes up to the polymer was studied using dielectric spectroscopy. The photophysical properties of OFn and PF2/6 were investigated by the steady-state spectra (UV-vis absorption and fluorescence spectra) and time-resolved fluorescence spectra both in solution and thin film. The time-resolved fluorescence spectra of the oligofluorenes were measured by streak camera and gate detection technique. The lifetime of the oligofluorenes decreased with the extension of the chain-length. No green emission was observed in CW, prompt and delayed fluorescence for oligofluorenes in m-THF and film at RT and 77K. Phosphorescence was observed for oligofluorenes in frozen dilute m-THF solution at 77K and its lifetime increased with length of oligofluorenes. A linear relation was obtained for triplet energy and singlet energy as a function of the reciprocal degree of polymerization, and the singlet-triplet energy gap (S1-T1) was found to decrease with the increase of degree of polymerization. Oligofluorenes with one fluorenone unit at the center were used as model compounds to understand the origin of the low-energy (“green”) emission band in the photoluminescence and electroluminescence spectra of polyfluorenes. Their electrochemical properties were investigated by CV, and the ionization potential (Ip) and electron affinity (Ea) were calculated from the onset of oxidation and reduction of OFnK. The photophysical properties of OFnK were studied in dilute solution and thin film by steady-state spectra and time-resolved fluorescence spectra. A strong green emission accompanied with a weak blue emission were obtained in solution and only green emission was observed on film. The strong green emission of OFnK suggested that rapid energy transfer takes place from higher energy sites (fluorene segments) to lower energy sites (fluorenone unit) prior to the radiative decay of the excited species. The fluorescence spectra of OFnK also showed solvatochromism. Monoexponential decay behaviour was observed by time-resolved fluorescence measurements. In addition, the site-selective excitation and concentration dependence of the fluorescence spectra were investigated. The ratio of green and blue emission band intensities increases with the increase of the concentration. The observed strong concentration dependence of the green emission band in solution suggests that increased interchain interactions among the fluorenone-containing oligofluorene chain enhanced the emission from the fluorenone defects at higher concentration. On the other hand, the mono-exponential decay behaviour and power dependence were not influenced significantly by the concentration. We have ruled out the possibility that the green emission band originates from aggregates or excimer formation. Energy transfer was further investigated using a model system of a polyfluorene doped by OFnK. Förster-type energy transfer took place from PF2/6 to OFnK, and the energy transfer efficiency increased with increasing of the concentration of OFnK. Efficient funneling of excitation energy from the high-energy fluorene segments to the low-energy fluorenone defects results from energy migration by hopping of excitations along a single polymer chain until they are trapped on the fluorenone defects on that chain or transferred onto neighbouring chains by Förster-type interchain energy transfer process. These results imply that the red-shifted emission in polyfluorenes can originate from (usually undesirable) keto groups at the bridging carbon atoms-especially if the samples have been subject to photo- or electro-oxidation or if fluorenone units are present due to an improper purification of the monomers prior to polymerization.

Thermal relaxation for particle systems in interaction with several bosonic heat reservoirs

The present thesis is concerned with the study of a quantum physical system composed of a small particle system (such as a spin chain) and several quantized massless boson fields (as photon gasses or phonon fields) at positive temperature. The setup serves as a simplified model for matter in interaction with thermal "radiation" from different sources. Hereby, questions concerning the dynamical and thermodynamic properties of particle-boson configurations far from thermal equilibrium are in the center of interest. We study a specific situation where the particle system is brought in contact with the boson systems (occasionally referred to as heat reservoirs) where the reservoirs are prepared close to thermal equilibrium states, each at a different temperature. We analyze the interacting time evolution of such an initial configuration and we show thermal relaxation of the system into a stationary state, i.e., we prove the existence of a time invariant state which is the unique limit state of the considered initial configurations evolving in time. As long as the reservoirs have been prepared at different temperatures, this stationary state features thermodynamic characteristics as stationary energy fluxes and a positive entropy production rate which distinguishes it from being a thermal equilibrium at any temperature. Therefore, we refer to it as non-equilibrium stationary state or simply NESS. The physical setup is phrased mathematically in the language of C*-algebras. The thesis gives an extended review of the application of operator algebraic theories to quantum statistical mechanics and introduces in detail the mathematical objects to describe matter in interaction with radiation. The C*-theory is adapted to the concrete setup. The algebraic description of the system is lifted into a Hilbert space framework. The appropriate Hilbert space representation is given by a bosonic Fock space over a suitable L2-space. The first part of the present work is concluded by the derivation of a spectral theory which connects the dynamical and thermodynamic features with spectral properties of a suitable generator, say K, of the time evolution in this Hilbert space setting. That way, the question about thermal relaxation becomes a spectral problem. The operator K is of Pauli-Fierz type. The spectral analysis of the generator K follows. This task is the core part of the work and it employs various kinds of functional analytic techniques. The operator K results from a perturbation of an operator L0 which describes the non-interacting particle-boson system. All spectral considerations are done in a perturbative regime, i.e., we assume that the strength of the coupling is sufficiently small. The extraction of dynamical features of the system from properties of K requires, in particular, the knowledge about the spectrum of K in the nearest vicinity of eigenvalues of the unperturbed operator L0. Since convergent Neumann series expansions only qualify to study the perturbed spectrum in the neighborhood of the unperturbed one on a scale of order of the coupling strength we need to apply a more refined tool, the Feshbach map. This technique allows the analysis of the spectrum on a smaller scale by transferring the analysis to a spectral subspace. The need of spectral information on arbitrary scales requires an iteration of the Feshbach map. This procedure leads to an operator-theoretic renormalization group. The reader is introduced to the Feshbach technique and the renormalization procedure based on it is discussed in full detail. Further, it is explained how the spectral information is extracted from the renormalization group flow. The present dissertation is an extension of two kinds of a recent research contribution by Jakšić and Pillet to a similar physical setup. Firstly, we consider the more delicate situation of bosonic heat reservoirs instead of fermionic ones, and secondly, the system can be studied uniformly for small reservoir temperatures. The adaption of the Feshbach map-based renormalization procedure by Bach, Chen, Fröhlich, and Sigal to concrete spectral problems in quantum statistical mechanics is a further novelty of this work.

Probing strongly correlated states of ultracold atoms in optical lattices

This thesis describes experiments which investigate ultracold atom ensembles in an optical lattice. Such quantum gases are powerful models for solid state physics. Several novel methods are demonstrated that probe the special properties of strongly correlated states in lattice potentials. Of these, quantum noise spectroscopy reveals spatial correlations in such states, which are hidden when using the usual methods of probing atomic gases. Another spectroscopic technique makes it possible to demonstrate the existence of a shell structure of regions with constant densities. Such coexisting phases separated by sharp boundaries had been theoretically predicted for the Mott insulating state. The tunneling processes in the optical lattice in the strongly correlated regime are probed by preparing the ensemble in an optical superlattice potential. This allows the time-resolved observation of the tunneling dynamics, and makes it possible to directly identify correlated tunneling processes.

Stable laser and upgraded vacuum setup for an experiment with ultracold atoms

In questo lavoro ci si propone di descrivere la realizzazione di un sistema laser con cavit´a esterna e di un apparato da ultra-alto-vuoto, che verranno impiegati in un esperimento di miscele di atomi ultrafreddi che utilizza due specie atomiche di bosoni: 87Rb e 41K. Speciale attenzione viene rivolta verso le caratteristiche dello schema utilizzato e sul sistema di controllo in temperatura, che rendono questo sistema laser particolarmente stabile in frequenza e insensibile alle vibrazioni e variazioni di temperatura. Si sono poi analizzate le propriet´a dei materiali impiegati e delle procedure sperimentali adottate per la realizzazione del nuovo apparato da vuoto, al fine di garantire migliori prestazioni rispetto al sistema attualmente in uso.