Spectroscopic Characterization and Modeling of Quadrupolar Charge-Transfer Dyes with Bulky Substituents

Joint experimental and theoretical work is presented on two quadrupolar D-pi-A-pi-D chromophores characterized by the same bulky donor (D) group and two different central cores. The first chromophore, a newly synthesized species with a malononitrile-based acceptor (A) group, has a V-shaped structure that makes its absorption spectrum very broad, covering most of the visible region. The second chromophore has a squaraine-based core and therefore a linear structure, as also evinced from its absorption spectra. Both chromophores show an anomalous red shift of the absorption band upon increasing solvent polarity, a feature that is ascribed to the large, bulky structure of the moleCules. For these molecules, the basic description of polar solvation in terms of a uniform reaction field fails. Indeed, a simple extension of the model to account for two independent reaction fields associated with the two molecular arms quantitatively reproduces the observed linear absorption and fluorescence as well as fluorescence anisotropy spectra, fully rationalizing their nontrivial dependence on solvent polarity. The model derived from the analysis of linear spectra is adopted to predict nonlinear spectra and specifically hyper-Rayleigh scattering and two-photon absorption spectra. In polar solvents, the V-shaped chromophore is predicted to have a large HRS response in a wide spectral region (approximately 600-1300 nm). Anomalously large and largely solvent-dependent HRS responses for the linear chromophores are ascribed to symmetry lowering induced by polar solvation and amplified in this bulky system by the presence of two reaction fields.

Fermi-edge singularity in photoluminescence spectra of modulation-doped AlGaAs/InGaAs/GaAs quantum wells

The photoluminescence study of Fermi-edge singularity (FES) in modulation-doped pseudomorphic AlxGa1-xAs/InyGa1-yAs/GaAs quantum well (QW) heterostructures is presented. In the above QW structures the optical transitions between n = 1 and n = 2 electronic subband to the n = 1 heavy hole subband (E-11 and E-21 transitions, respectively) are observed with FES appearing as a lower energy shoulder to the E-21 transition. The observed FES is attributed to the Fermi wave vector in the first electronic subband under the conditions of population of the second electronic subband. The FES appears at about 10 meV below E-21 transition around 4.2 K. Initially it gets stronger with increasing temperature and becomes a distinct peak at about 20 K. Further increase in temperature quenches FES and reaches the base line at around 40 K.

Ultrasound Assisted Optical Tomography: Estimation of phase Shift experienced by photon on transit through US insonified region for detection of breast tumor

A Monte Carlo model of ultrasound modulation of multiply scattered coherent light in a highly scattering media has been carried out for estimating the phase shift experienced by a photon beam on its transit through US insonified region. The phase shift is related to the tissue stiffness, thereby opening an avenue for possible breast tumor detection. When the scattering centers in the tissue medium is exposed to a deterministic forcing with the help of a focused ultrasound (US) beam, due to the fact that US-induced oscillation is almost along particular direction, the direction defined by the transducer axis, the scattering events increase, thereby increasing the phase shift experienced by light that traverses through the medium. The phase shift is found to increase with increase in anisotropy g of the medium. However, as the size of the focused region which is the region of interest (ROI) increases, a large number of scattering events take place within the ROI, the ensemble average of the phase shift (Delta phi) becomes very close to zero. The phase of the individual photon is randomly distributed over 2 pi when the scattered photon path crosses a large number of ultrasound wavelengths in the focused region. This is true at high ultrasound frequency (1 MHz) when mean free path length of photon l(s) is comparable to wavelength of US beam. However, at much lower US frequencies (100 Hz), the wavelength of sound is orders of magnitude larger than l(s), and with a high value of g (g 0.9), there is a distinct measurable phase difference for the photon that traverses through the insonified region. Experiments are carried out for validation of simulation results.

Feasibility study of the measurement of Higgs pair creation at a photon linear collider

We studied the feasibility of the measurement of Higgs pair creation at a photon linear collider. From the sensitivity to the anomalous self-coupling of the Higgs boson, the optimum gamma gamma collision energy was found to be around 270 GeV for a Higgs mass of 120 GeV/c(2). We found that large backgrounds such as gamma gamma -> W+W-, ZZ, and b (b) over barb (b) over bar can be suppressed if correct assignment of tracks to parent partons is achieved and Higgs pair events can be observed with a statistical significance of similar to 5 sigma by operating the photon linear collider for 5 years.

Study of molecular structure and vibrational spectra of poly (beta,-1-malic acid) PMLA] using DFT approach

Poly (beta-L-malic acid) (PMLA) is a biodegradable polymer and it has various important applications in the biomedical field. In the present work the structural and spectral characteristics of PMLA have been studied by methods of infrared. Raman spectroscopy and quantum chemistry. Electrostatic potential surface, optimized geometry, harmonic vibrational frequencies, infrared intensities and activities of Raman scattering were calculated by density functional theory (DFT) using oligomeric approach employing B3LYP with complete relaxation in the potential energy surface using 6-311++G (d, p) basis set. Based on results, we have discussed the correlation between the vibrational modes and the structure of the PMLA. A complete analysis of the experimental infrared and Raman spectra has been reported on the basis of wavenumber of the vibrational bands and potential energy distribution. The calculated HOMO and LUMO energies shows that charge transfer occur within the molecule. The calculated infrared and the Raman spectra of the polymer based on DFT calculations show reasonable agreement with the experimental results. (c) 2012 Elsevier Ltd. All rights reserved.

Infrared Spectra of Dimethylphenanthrenes in the Gas phase

Infrared spectra of atmospherically and astronomically important dimethylphenanthrenes (DMPs), namely 1,9-DMP, 2,4-DMP, and 3,9-DMP, were recorded in the gas phase from 400 to 4000 cm(-1) with a resolution of 0.5 cm(-1) at 110 degrees C using a 7.2 m gas cell. DFT calculations at the B3LYP/6-311G** level were carried out to get the harmonic and anharmonic frequencies and their corresponding intensities for the assignment of the observed bands. However, spectral assignments could not be made unambiguously using anharmonic or selectively scaled harmonic frequencies. Therefore, the scaled quantum mechanical (SQM) force field analysis method was adopted to achieve more accurate assignments. In this method force fields instead of frequencies were scaled. The Cartesian force field matrix obtained from the Gaussian calculations was converted to a nonredundant local coordinate force field matrix and then the force fields were scaled to match experimental frequencies in a consistent manner using a modified version of the UMAT program of the QCPE package. Potential energy distributions (PEDs) of the normal modes in terms of nonredundant local coordinates obtained from these calculations helped us derive the nature of the vibration at each frequency. The intensity of observed bands in the experimental spectra was calculated using estimated vapor pressures of the DMPs. An error analysis of the mean deviation between experimental and calculated intensities reveal that the observed methyl C-H stretching intensity deviates more compared to the aromatic C-H and non C-H stretching bands.

Nonlinear Refraction and Two-Photon Absorption in Dense 2Bi(2)O(3)-B2O3 Glasses

High density transparent glasses (7.86 g/cc) were fabricated in the 2Bi(2)O(3)-B2O3 (BBO) system. Optical band gap of the obtained glasses was found to be 2.6eV. The refractive index measured for these glasses was 2.25 +/- 0.05 at lambda=543 nm. Nonlinear refraction and absorption studies were carried out on the BBO glasses using z-scan technique a lambda=532 nm of 10 ns pulse width. The nonlinear refractive index obtained was n(2)=12.1x10(-14) cm(2)/W and nonlinear absorption coefficient was beta=15.2 cm/GW. The n(2) and beta values of the BBO glasses were large compared to the other reported high index bismuth based oxide glass systems in the literature. These were attributed to the high density, high linear refractive index, low band gap and two photon absorption associated with these glasses. The electronic origin of large nonlinearities was discussed based on bond-orbital theory.

DFT study of structure and vibrational spectra of ceramide 3: comparison to experimental data

The Fourier transform Raman and infrared (IR) spectra of the Ceramide 3 (CER3) have been recorded in the regions 200-3500 cm(-1) and 680-4000 cm(-1), respectively. We have calculated the equilibrium geometry, harmonic vibrational wavenumbers, electrostatic potential surfaces, absolute Raman scattering activities and IR absorption intensities by the density functional theory with B3LYP functionals having extended basis set 6-311G. This work is undertaken to study the vibrational spectra of CER3 completely and to identify the various normal modes with better wavenumber accuracy. Good consistency is found between the calculated results and experimental data for the IR and Raman spectra.

SuSeFLAV: A program for calculating supersymmetric spectra and lepton flavour violation

The program SuSeFLAV is introduced for computing supersymmetric mass spectra with flavour violation in various supersymmetric breaking scenarios with/without see-saw mechanism. A short user guide summarizing the compilation, executables and the input files is provided.

Large nonlinear refraction and two photon absorption in ferroelectric Bi2VO5.5 thin films

Ferroelectric c-oriented Bi2VO5.5 (BVO) thin films (thickness approximate to 300 nm) were fabricated by pulsed laser deposition on corning glass substrates. Nonlinear refractive index (n(2)) and two photon absorption coefficient (beta) were measured by Z-scan technique at 532 nm wavelength delivering pulses with 10 ns duration. Relatively large values of n(2) = 2.05 +/- 0.2 x 10(-10) cm(2)/W and beta = 9.36 +/- 0.3 cm/MW were obtained for BVO thin films. Origin of the large optical nonlinearities in BVO thin films was discussed based on bond-orbital theory of transition metal oxides. (c) 2012 Elsevier B.V. All rights reserved.

Influence of annealing temperature on Raman and photoluminescence spectra of electron beam evaporated TiO2 thin films

Titanium dioxide (TiO2) thin films were deposited on fused quartz substrates by electron beam evaporation method at room temperature. The films were annealed at different temperatures in ambient air. The surface morphology/roughness at different annealing temperatures were analyzed by atomic force microscopy (AFM). The crystallinity of the film has improved with the increase of annealing temperature. The effect of annealing temperature on optical, photoluminescence and Raman spectra of TiO2 films were investigated. The refractive index of TiO2 films were studied by envelope method and reflectance spectra and it is observed that the refractive index of the films was high. The photoluminescence intensity corresponding to green emission was enhanced with increase of annealing temperature. The peaks in Raman spectra depicts that the TiO2 film is of anatase phase after annealing at 300 degrees C and higher. The films show high refractive index, good optical quality and photoluminescence characteristics suggest that possible usage in opto-electronic and optical coating applications. (C) 2012 Elsevier B.V. All rights reserved.

Time-Temperature Scaling of Conductivity Spectra of Organic Plastic Crystalline Conductors

Organic plastic crystalline soft matter ion conductors are interesting alternatives to liquid electrolytes in electrochemical storage devices such as Lithium-ion batteries. The solvent dynamics plays a major role in determining the ion transport in plastic crystalline ion conductors. We present here an analysis of the frequency-dependent ionic conductivity of succinonitrile-based plastic crystalline ion conductors at varying salt composition (0.005 to 1 M) and temperature (-20 to 60 degrees C) using time-temperature superposition principle (TTSP). The main motivation of the work has been to establish comprehensive insight into the ion transport mechanism from a single method viz, impedance spectroscopy rather than employing cluster of different characterization methods probing various length and time scales. The TTSP remarkably aids in explicit identification of the extent of the roles of solvent dynamics and ion-ion interactions on the effective conductivity of the orientationally disordered plastic crystalline ion conductors.

Two-Dimensional Correlation Analysis of Temperature-Dependent FT-IR Spectra of Oleic Acid

In the present study, variable temperature FT-IR spectroscopic investigations were used to characterize the spectral changes in oleic acid during heating oleic acid in the temperature range from -30 degrees;C to 22 degrees C. In order to extract more information about the spectral variations taking place during the phase transition process, 2D correlation spectroscopy (2DCOS) was employed for the stretching (C?O) and rocking (CH2) band of oleic acid. However, the interpretation of these spectral variations in the FT-IR spectra is not straightforward, because the absorption bands are heavily overlapped and change due to two processes: recrystallization of the ?-phase and melting of the oleic acid. Furthermore, the solid phase transition from the ?- to the a-phase was also observed between -4 degrees C and -2 degrees C. Thus, for a more detailed 2DCOS analysis, we have split up the spectral data set in the subsets recorded between -30 degrees C to -16 degrees C, -16 degrees C to 10 degrees C, and 10 degrees C to 22 degrees C. In the corresponding synchronous and asynchronous 2D correlation plots, absorption bands that are characteristic of the crystalline and amorphous regions of oleic acid were separated.

Real-Space Manifestations of Bottlenecks in Turbulence Spectra

An energy-spectrum bottleneck, a bump in the turbulence spectrum between the inertial and dissipation ranges, is shown to occur in the nonturbulent, one-dimensional, hyperviscous Burgers equation and found to be the Fourier-space signature of oscillations in the real-space velocity, which are explained by boundary-layer-expansion techniques. Pseudospectral simulations are used to show that such oscillations occur in velocity correlation functions in one- and three-dimensional hyperviscous hydrodynamical equations that display genuine turbulence. DOI: 10.1103/PhysRevLett.110.064501