Measuring The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy.

Fluorescence Correlation Spectroscopy (FCS) is an optical technique that allows the measurement of the diffusion coefficient of molecules in a diluted sample. From the diffusion coefficient it is possible to calculate the hydrodynamic radius of the molecules. For colloidal quantum dots (QDs) the hydrodynamic radius is valuable information to study interactions with other molecules or other QDs. In this chapter we describe the main aspects of the technique and how to use it to calculate the hydrodynamic radius of quantum dots (QDs).

Atomic Charge Transfer-counter Polarization Effects Determine Infrared Ch Intensities Of Hydrocarbons: A Quantum Theory Of Atoms In Molecules Model.

Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

Interplay Of Weak Interactions In The Atom-by-atom Condensation Of Xenon Within Quantum Boxes.

Condensation processes are of key importance in nature and play a fundamental role in chemistry and physics. Owing to size effects at the nanoscale, it is conceptually desired to experimentally probe the dependence of condensate structure on the number of constituents one by one. Here we present an approach to study a condensation process atom-by-atom with the scanning tunnelling microscope, which provides a direct real-space access with atomic precision to the aggregates formed in atomically defined 'quantum boxes'. Our analysis reveals the subtle interplay of competing directional and nondirectional interactions in the emergence of structure and provides unprecedented input for the structural comparison with quantum mechanical models. This approach focuses on-but is not limited to-the model case of xenon condensation and goes significantly beyond the well-established statistical size analysis of clusters in atomic or molecular beams by mass spectrometry.

Measurement Of The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy Excluding Blinking.

One of the most important properties of quantum dots (QDs) is their size. Their size will determine optical properties and in a colloidal medium their range of interaction. The most common techniques used to measure QD size are transmission electron microscopy (TEM) and X-ray diffraction. However, these techniques demand the sample to be dried and under a vacuum. This way any hydrodynamic information is excluded and the preparation process may alter even the size of the QDs. Fluorescence correlation spectroscopy (FCS) is an optical technique with single molecule sensitivity capable of extracting the hydrodynamic radius (HR) of the QDs. The main drawback of FCS is the blinking phenomenon that alters the correlation function implicating in a QD apparent size smaller than it really is. In this work, we developed a method to exclude blinking of the FCS and measured the HR of colloidal QDs. We compared our results with TEM images, and the HR obtained by FCS is higher than the radius measured by TEM. We attribute this difference to the cap layer of the QD that cannot be seen in the TEM images.

Photophysical properties and quantum chemical studies of poly(2,7-9,9'-dihexylfluorene-dyil)

This work reports the photophysical properties (excitation and fluorescence spectra, fluorescence quantum yield, fluorescence lifetimes) of the poly(2,7-9,9'-dihexylfluorene-dyil) in dilute solutions of four solvents (toluene, tetrahydrofuran, chloroform and ethyl acetate) as well as the properties in solid state. Photoluminescence showed spectra characteristic of disordered α-backbone chain conformation. Simulation of the electronic absorption spectra of oligomers containing 1 to 11 mers showed that the critical conjugation length is between 6 and 7 mers. We also estimated the theoretical dipole moments which indicated that a coil conformation is formed with 8 repeating units per turn. We also showed that some energy transfer process appears in solid state which decreases the emission lifetime. Furthermore, based on luminescent response of the systems herein studied and electroluminescent behavior reported on literature, both photo and electroluminescence emissions arise from the same emissive units.

Uma perspectiva computacional sobre catálise enzimática

Enzymes are extremely efficient catalysts. Here, part of the mechanisms proposed to explain this catalytic power will be compared to quantitative experimental results and computer simulations. Influence of the enzymatic environment over species along the reaction coordinate will be analysed. Concepts of transition state stabilisation and reactant destabilisation will be confronted. Divided site model and near-attack conformation hypotheses will also be discussed. Molecular interactions such as covalent catalysis, general acid-base catalysis, electrostatics, entropic effects, steric hindrance, quantum and dynamical effects will also be analysed as sources of catalysis. Reaction mechanisms, in particular that catalysed by protein tyrosine phosphatases, illustrate the concepts.

Architecture for machining process and production monitoring based in open computer numerical control

This paper proposes an architecture for machining process and production monitoring to be applied in machine tools with open Computer numerical control (CNC). A brief description of the advantages of using open CNC for machining process and production monitoring is presented with an emphasis on the CNC architecture using a personal computer (PC)-based human-machine interface. The proposed architecture uses the CNC data and sensors to gather information about the machining process and production. It allows the development of different levels of monitoring systems with mininium investment, minimum need for sensor installation, and low intrusiveness to the process. Successful examples of the utilization of this architecture in a laboratory environment are briefly described. As a Conclusion, it is shown that a wide range of monitoring solutions can be implemented in production processes using the proposed architecture.

Dynamical models for computer viruses propagation

Nowadays, digital computer systems and networks are the main engineering tools, being used in planning, design, operation, and control of all sizes of building, transportation, machinery, business, and life maintaining devices. Consequently, computer viruses became one of the most important sources of uncertainty, contributing to decrease the reliability of vital activities. A lot of antivirus programs have been developed, but they are limited to detecting and removing infections, based on previous knowledge of the virus code. In spite of having good adaptation capability, these programs work just as vaccines against diseases and are not able to prevent new infections based on the network state. Here, a trial on modeling computer viruses propagation dynamics relates it to other notable events occurring in the network permitting to establish preventive policies in the network management. Data from three different viruses are collected in the Internet and two different identification techniques, autoregressive and Fourier analyses, are applied showing that it is possible to forecast the dynamics of a new virus propagation by using the data collected from other viruses that formerly infected the network. Copyright (c) 2008 J. R. C. Piqueira and F. B. Cesar. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Multiple classical limits in relativistic and nonrelativistic quantum mechanics

The existence of a classical limit describing the interacting particles in a second-quantized theory of identical particles with bosonic symmetry is proved. This limit exists in addition to the previously established classical limit with a classical field behavior, showing that the limit h -> 0 of the theory is not unique. An analogous result is valid for a free massive scalar field: two distinct classical limits are proved to exist, describing a system of particles or a classical field. The introduction of local operators in order to represent kinematical properties of interest is shown to break the permutation symmetry under some localizability conditions, allowing the study of individual particle properties.

Quantum statistical correlations in thermal field theories: Boundary effective theory

We show that the one-loop effective action at finite temperature for a scalar field with quartic interaction has the same renormalized expression as at zero temperature if written in terms of a certain classical field phi(c), and if we trade free propagators at zero temperature for their finite-temperature counterparts. The result follows if we write the partition function as an integral over field eigenstates (boundary fields) of the density matrix element in the functional Schrodinger field representation, and perform a semiclassical expansion in two steps: first, we integrate around the saddle point for fixed boundary fields, which is the classical field phi(c), a functional of the boundary fields; then, we perform a saddle-point integration over the boundary fields, whose correlations characterize the thermal properties of the system. This procedure provides a dimensionally reduced effective theory for the thermal system. We calculate the two-point correlation as an example.

Study of the influence of indium segregation on the optical properties of InGaAs/GaAs quantum wells via split-operator method

In the case of quantum wells, the indium segregation leads to complex potential profiles that are hardly considered in the majority of the theoretical models. The authors demonstrated that the split-operator method is useful tool for obtaining the electronic properties in these cases. Particularly, they studied the influence of the indium surface segregation in optical properties of InGaAs/GaAs quantum wells. Photoluminescence measurements were carried out for a set of InGaAs/GaAs quantum wells and compared to the results obtained theoretically via split-operator method, showing a good agreement.

Growth and capping of InAs/GaAs quantum dots investigated by x-ray Bragg-surface diffraction

An x-ray diffraction method, based on the excitation of a surface diffracted wave, is described to investigate the capping process of InAs/GaAs (001) quantum dots (QDs). It is sensitive to the tiny misorientation of (111) planes at the surface of the buffer layer on samples with exposed QDs. After capping, the misorientation occurs in the cap-layer lattice faceting the QDs and its magnitude can be as large as 10 degrees depending on the QDs growth rates, probably due to changes in the size and shape of the QDs. A slow strain release process taking place at room temperature has also been observed by monitoring the misorientation angle of the (111) planes.

Electron dephasing scattering rate in two-dimensional GaAs/InGaAs heterostructures with embedded InAs quantum dots

We report a comprehensive study of weak-localization and electron-electron interaction effects in a GaAs/InGaAs two-dimensional electron system with nearby InAs quantum dots, using measurements of the electrical conductivity with and without magnetic field. Although both the effects introduce temperature dependent corrections to the zero magnetic field conductivity at low temperatures, the magnetic field dependence of conductivity is dominated by the weak-localization correction. We observed that the electron dephasing scattering rate tau(-1)(phi), obtained from the magnetoconductivity data, is enhanced by introducing quantum dots in the structure, as expected, and obeys a linear dependence on the temperature and elastic mean free path, which is against the Fermi-liquid model. (c) 2008 American Institute of Physics. [DOI: 10.1063/1.2996034]

Numerical investigation of the quantum fluctuations of optical fields transmitted through an atomic medium

We have numerically solved the Heisenberg-Langevin equations describing the propagation of quantized fields through an optically thick sample of atoms. Two orthogonal polarization components are considered for the field, and the complete Zeeman sublevel structure of the atomic transition is taken into account. Quantum fluctuations of atomic operators are included through appropriate Langevin forces. We have considered an incident field in a linearly polarized coherent state (driving field) and vacuum in the perpendicular polarization and calculated the noise spectra of the amplitude and phase quadratures of the output field for two orthogonal polarizations. We analyze different configurations depending on the total angular momentum of the ground and excited atomic states. We examine the generation of squeezing for the driving-field polarization component and vacuum squeezing of the orthogonal polarization. Entanglement of orthogonally polarized modes is predicted. Noise spectral features specific to (Zeeman) multilevel configurations are identified.