MDS codec evaluation based on perceptual sound attributes

The present paper deals with the subjective evaluation of audio coding technologies using the “Similarity Rating” psychometric method. Compressed audio excerpts are presented to a group of experienced listeners by pairs of stimuli. Each pair represents a different type of distortion, with compression included. These types of distortion correspond to three psychoacoustic attributes, sharpness, roughness, and fluctuation strength. Listener’s task is to evaluate the degree of similarity between the pairs. The final output is the localization of each measured codec in this psychoacoustic space. Multidimensional scaling is the statistic technique, belonging to Multivariate Statistical methods, which allows processing the results obtained from this method

Understanding the two-photon absorption spectrum of PE2 platinum acetylide complex

Herein, we report on the two-absorption cross-section spectrum of trans-Pt(PBu3)2 (C≡C-C6H4-C≡C-C6H5)2 (PE2) platinum acetylide complex employing the femtosecond wavelength-tunable Z-scan technique. The PE2 complex can be visualized as two branches containing two phenylacetylene units, each one linked by a platinum center, completely transparent in the visible region. Because of this structure, large delocalization of π-electrons allied to the strong intramolecular interaction between the branches is expected. The 2PA absorption spectrum was measured using the femtosecond wavelength-tunable Z-scan technique with low repetition rate (1 kHz), in order to obtain the 2PA spectrum without excited-state contributions. Our results reveal that PE2 in dichloromethane solution presents two 2PA allowed bands located at 570 and 710 nm, with cross section of about 320 and 45 GM, respectively. The first one is related to the strong intramolecular interaction between the molecule’s branches due to the presence of platinum atom, while the second one is associated with the breaking of symmetry of the chromophore in solution due, most probably to a large twisting angle of the ligand’s phenyl rings relative to the Pt core.FAPESP (11/06489-6; 11/12399-0)CNPqCAPESAFOSR (FA9550-12-1-0028

Femtosecond two-photon absorption spectroscopy of poly(fluorene) derivatives containing benzoselenadiazole and benzothiadiazole

We have investigated the molecular structure and two-photon absorption (2PA) properties relationship of two push-pull poly(fluorene) derivatives containing benzoselenadiazole and benzothiadiazole units. For that, we have used the femtosecond wavelength-tunable Z-scan technique with a low repetition rate (1 kHz) and an energy per pulse on the order of nJ. Our results show that both 2PA spectra present a strong 2PA (around 600 GM (1 GM = 1×10-50 cm4 .s. photon-1)) band at around 720 nm (transition energy 3.45 eV) ascribed to the strongly 2PA-allowed 1Ag-like → mAg-like transition, characteristic of poly(fluorene) derivatives. Another 2PA band related to the intramolecular charge transfer was also observed at around 900 nm (transition energy 2.75 eV). In both 2PA bands, we found higher 2PA cross-section values for the poly(fluorene) containing benzothiadiazole unit. This outcome was explained through the higher charge redistribution at the excited state caused by the benzothiadiazole group as compared to the benzoselenadiazole and confirmed by means of solvatochromic Stokes shift measurements. To shed more light on these results, we employed the sum-over-states approach within the two-energy level model to estimate the maximum permanent dipole moment change related to the intramolecular charge transfer transition

First-Order Hyperpolarizability Of Triphenylamine Derivatives Containing Cyanopyridine: Molecular Branching Effect

In the present work, we report the multibranching effect on the dynamic first-order hyperpolarizability (β(-2ω; ω, ω)) of triphenylamine derivatives containing cyanopyridine one-branch (dipolar structure), two-branch (V-shaped structure), and three-branch (octupolar structure) structures. For this study, we used the hyper-Rayleigh scattering (HRS) technique involving picosecond pulse trains at 1064 nm. Our results show that βHRS increases from 2.02 × 10-28 to 9.24 × 10-28 cm5/esu when an extra branch is added to the molecule, configuring a change from a dipolar to a V-shaped (quadrupolar) molecular structure. When a third branch is added, leading to an octupolar structure, a decrease to 3.21 × 10-28 cm5/esu is observed. Such a significant decrease in βHRS is attributed to a negative contribution presented in the βHRS description by using a three-level energy approach due to their electronic structure and considering a specific combination of the angle between the dipole moments. On the other hand, the enhancement of βHRS found for the quadrupolar structure is associated with the cooperative enhancement due to the electronic coupling between the branches that increases considerably the transition dipole moment and permanent dipole moment change. To explain the βHRS results obtained for different molecules, we employed the HRS figure of merit, FOMHRS = βHRS/Neff 3/2, in which Neff is the effective number of π-conjugated bonds, and the few-energy level approach for βHRS within the Frenkel exciton model. To shed more light on the experimental results interpretation, we performed time-dependent density functional theory calculations combined with a polarizable continuum model to confirm the energy and oscillator strength of the electronic transitions assumed in the Frenkel exciton model employed here

Femtosecond Two-Photon Absorption Spectroscopy Of Copper Indium Sulfide Quantum Dots: A Structure-Optical Properties Relationship

We have interpreted the two-photon absorption spectrum of water-soluble copper indium sulfide (CIS) QDs with stoichiometry 0.18 (Cu), 0.42 (In), and 2 (S) and an average diameter of approximately 2.6 nm. For that, we employed the wavelength-tunable femtosecond Z-scan technique and the parabolic effective-mass approximation model, in which the excitonic transition energies were phenomenologically corrected due to the stoichiometry of the nanocrystal. This model considers a conduction band and three valence sub-bands allowing excitonic transitions via centrosymmetric (Δl = ±1, where l is the angular momentum of the absorbing state) and non-centrosymmetric (Δl = 0) channels. In such case, this became relevant because the CIS QDs with chalcopyrite crystalline structure is a non-centrosymmetric semiconductor. Thus, our experimental results pointed out two 2 PA allowed bands located at 715 nm (2hv = 3.47 eV) and 625 nm (2hv = 3.97 eV) with cross sections of (6.3 ± 1.0) x 102 GM and (4.5 ± 0.7) x 102 GM, respectively. According to the theoretical model, these 2 PA bands can be ascribed to the 1P1/2(h3) → 1S3/2(e) (lower energy band) and 1P1/2(hheavy) → 1S3/2(e) (90%)/(10%)1P1/2(hsplit-off) → 1P3/2(e) (higher energy band) excitonic transitions. A good agreement (magnitude and spectral position) between the experimental and theoretical data were obtained. However, our experimental data suggest that the higher-energy 2 PA band may have other contributions due to the mixing between the heavy- and the light-hole bands, which the effective mass model does not take into consideration

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

Broadband three-photon absorption spectra of platinum acetylide complexes

We investigate the three-photon absorption spectra of four platinum acetylides complexes employing femtosecond pulses. We observed strong three-photon absorption cross-section in the near-infrared region (from 850 nm to 1200 nm). The three-photon absorption (3PA) spectra present resonance enhancement effect as two photons of the excitation wavelength approach the lower two-photon allowed states of the molecules as well as a 3PA allowed band around 1180 nm. The 3PA cross-section spectra were interpreted using the sum-over-essential-states approach, considering a three-energy-level diagram.FAPESPCNPqCAPESAFOSR (FA9550-07-1-0374

MDS codec evaluation based on perceptual sound attributes

The present paper deals with the subjective evaluation of audio coding technologies using the “Similarity Rating” psychometric method. Compressed audio excerpts are presented to a group of experienced listeners by pairs of stimuli. Each pair represents a different type of distortion, with compression included. These types of distortion correspond to three psychoacoustic attributes, sharpness, roughness, and fluctuation strength. Listener’s task is to evaluate the degree of similarity between the pairs. The final output is the localization of each measured codec in this psychoacoustic space. Multidimensional scaling is the statistic technique, belonging to Multivariate Statistical methods, which allows processing the results obtained from this method

MDS CODEC EVALUATION BASED ON PERCEPTUAL SOUND ATTRIBUTES

The present paper deals with the subjective evaluation of audio coding technologies using the “Similarity Rating” psychometric method. Compressed audio excerpts are presented to a group of experienced listeners by pairs of stimuli. Each pair represents a different type of distortion, with compression included. These types of distortion correspond to three psychoacoustic attributes, sharpness, roughness, and fluctuation strength. Listener’s task is to evaluate the degree of similarity between the pairs. The final output is the localization of each measured codec in this psychoacoustic space. Multidimensional scaling is the statistic technique, belonging to Multivariate Statistical methods, which allows processing the results obtained from this method