Photoluminescence of 1,3-Diphenyl-1H-pyrazolo[3,4-b]quinoline and its derivatives: Experiment and quantum chemical simulations

The optical absorption and photoluminescent spectra are studied in recently synthesized diphenyl pyrazoloquinolines (DPPQ): 1,3-diphenyl-1H-pyrazolo[3,4-b] quinoline and its 6-vinyl, 6-N,N-diphenyl, 6-methyl, 6-fluoro, 6-bromo and 6-chloro derivatives. The photoemission spectra are recorded in organic solvents of different polarity and found to be highly solvatochromic. The measured spectra are compared with the quantum chemical calculations performed by means of the semiempirical methods (AM1 or PM3) in combination with the equilibrium molecular conformation (EMC) in vacuo (T = 0 K, Γ = 0.12 eV) or MD simulations (T = 300 K). The broadening of absorption and emission bands and their red-shift with increasing of temperature may be well reproduced by MD simulations. The Stokes shift of the photoluminescent spectra is obtained by including vibrational modes into the emission equation. The quantum chemical method AM1 in combination with MD simulations gives in most cases the best agreement with the experimental data. By comparing the emission spectra of 6-N,N-diphenyl-DPPQ with other DPPQ-derivatives one concludes that the molecular fragment diphenyl-amin [(C₆H₅)₂N-] is likely subjected to strong conformational changes in solvents. The large difference between the excited- and state-dipole moments indicates on a strong electron transfer effect being common for all DPPQ derivatives.     

Optical absorption of 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its derivatives

Paper deals with the experimental investigations and quantum chemical calculations of the absorption spectra of newly synthesized 1,3-diphenyl-1H-Pyrazolo[3,4-b]quinoline and its 6-Vinyl, 6-N,N-Diphenyl, 6-Methyl, 6-Fluoro, 6-Bromo, and 6-Chloro derivatives. The calculations are performed by means of the semiempirical quantum chemical methods AM1 or PM3 combined with: (a) equilibrium molecular conformation (EMC) in vacuo; (b) the molecular conformation model considering a dynamical rotation of phenyl rings only (T = 300 K); and (c) the most general model of the conformational molecular dynamics (MD) at T = 300 K. It is shown that the phenyl dynamics appears to be not important in the spectral position of absorption thresholds as well as in a broadening of most absorbtion bands. On the other hand, the MD simulations reproduce a broadening of the absorbtion spectra as well as the electron-vibronic coupling leading to a red-shift of absorption bands with increasing of temperature. The conformational MD model in combination with the quantum chemical AM1 method gives in most cases the best agreement with the experimental data, namely in the sense of spectral positions and width of the absorption bands including first oscillators (absorption thresholds).     

Terahertz absorption spectrum of D2O vapor

The absorption spectrum of D₂O vapor from 0.2 to 2.0 THz (6.7-67 cm⁻¹) which is associated with rotational modes was measured at one atmosphere using terahertz time-domain spectroscopy (THz-TDS). The linewidth and collisional dephasing times were measured for 26 pure rotational transitions in the ground vibrational state (0 0 0). The temperature dependence of the linewidth (Δν) behaves as Δν ∼ T^−3/4 and the linewidth decrease with increasing temperature is attributed to the 1/r⁶ force of interaction between colliding D₂O molecules.     

Systematic analysis of the Fourier transform spectrum of CH3OH between 400 and 950 cm

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the ¹³CH₃OH isotopomer of methanol from 400 to 950 cm⁻¹ with the “Ritz” program. We present the assignments of 7160 transitions, 3021 of which belong to A-symmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The “Ritz” program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10⁻⁴ cm⁻¹. All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state.     

Optical gain and threshold properties of strained InGaAlAs/AlGaAs quantum wells for 850-nm vertical-cavity surface-emitting lasers

The valence subband structures, optical gain spectra, transparency carrier densities, and transparency radiative current densities of different compressively strained InGaAlAs quantum wells with Al_0.3Ga_0.7As barriers are systematically investigated using a 6 × 6 k · p Hamiltonian including the heavy hole, light hole, and spin-orbit splitting bands. The results of numerical calculations show that the maximum optical gain, transparency carrier densities, transparency radiative current densities, and differential gain of InGaAlAs quantum wells can be enhanced by introducing more compressive strain in quantum wells. However, further improvement of the optical properties of InGaAlAs quantum wells becomes minimal when the compressive strain is higher than approximately 1.5%. The simulation results suggest that the compressively strained InGaAlAs quantum wells are of advantages for application in high-speed 850-nm vertical-cavity surface-emitting lasers.     

Comparative investigations of the P-V-T relationship of NaCl at high pressure and temperature

Two different potential models of molecular dynamics (MD) simulations have been applied to investigate the pressure-volume-temperature (P-V-T) relationship and lattice parameter of NaCl under high pressure and temperature. The first one is the shell model (SM) potentials in which due to the short-range interaction pairs of ions are moved together as is the case in polarization of a crystal due to the motion of the positive and negative ions, and the second one is the two-body rigid-ion Born-Mayer-Huggins-Fumi-Tosi (BMHFT) potentials with full treatment of long-range Coulomb forces. The P-V relationship at 300 K, T-V relationship at zero pressure, and lattice parameter a, have been obtained and compared with the available experimental data and other theoretical results. Compared with SM potentials, the MD simulation with BMHFT potentials is very successful in reproducing accurately the measured volumes of NaCl. At an extended pressure and temperature ranges, P-V relationship under different isotherms at selected temperatures, T-V relationship under different pressures, and lattice parameter a have also been predicted. The properties of NaCl are summarized in the pressure range 0-30 GPa and the temperature up to 2000 K.     

FT-FIR-spectrum and the ground state constants of D2CO

The ground state spectrum of the formaldehyde D₂¹³CO molecule in the range from 25 to 360 cm⁻¹ has been recorded by a Fourier transform infrared spectrometer. The quantum number limits of the assigned transitions are J = 6-54 and K_a = 0-16. The data was fitted into Watson’s A- and S-reduced Hamiltonians in I^r-representation up to eighth order. The determinable constants calculated from both reductions are compared. The standard deviation of the far infrared data is 3.0 MHz. The spectroscopic constants are also calculated to high accuracy at the CCSD(T)/cc-pVQZ level of ab initio theory and agree well with the experimental ones.     

Adsorption model determination of N2O/Ag(1 1 0) by theoretical studies of near-edge X-ray absorption fine structure

The nitrogen 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of the N₂O adsorbed on Ag(1 1 0) have been studied by the multiple-scattering cluster (MSC) and self-consistent field (SCF) DV-Xα methods. Two adsorption models, in which the N₂O molecule attached to the Ag substrate through the central nitrogen (N_C) atom and the terminal nitrogen (N_T) atom, respectively, have been checked up thoroughly. The MSC calculation and the R-factor analysis show that the N₂O molecule is attached to the Ag substrate through the terminal nitrogen atom with the adsorption height h = 3.4 ± 0.1 Å. In the overlayer the N₂O molecules arrange themselves into a tilted chain due to the interaction between the cations and the anions in the molecules. The physical cause of the resonances in the NEXAFS spectra mentioned above has been discussed by the DV-Xα method, which confirms the MSC calculations.     

Low-temperature STM/STS studies on boron-doped (1 1 1) diamond films

We have performed scanning tunneling microscopy/spectroscopy (STM/STS) experiments on (1 1 1)-oriented epitaxial films of heavily boron-doped diamond (T_c∼5.4 K). We present that tunneling conductance spectra show temperature-dependent spatial variations. In the low-temperature region (T=0.47 K), the tunneling spectra do not show strong spatial dependence and a superconducting energy gap is observed independent of the surface morphology. In the high-temperature region (T=4.2 K), on the other hand, the tunneling conductance spectra show significant spatial dependence, indicating the inhomogeneous distribution of the superconducting property due to the distribution of boron atoms.     

Molecular dynamics simulation of P-V-T relationship of ZnO with rock-salt structure using pair-wise interactions

Molecular dynamics (MD) method is used to investigate the behavior of the pressure-volume-temperature (P-V-T) relationship, lattice constant and thermal expansivity for ZnO with rock-salt structure at high pressures and temperatures. The interionic potential is taken to be the sum of pair-wise additive Coulomb, van der Waals attraction, and repulsive interactions. The isothermal and isobaric properties are discussed from the corresponding P-V-T relationship, and it is shown that the MD simulation is successful in reproducing the measured volumes of ZnO over a wide range of temperature and pressure. Meanwhile, the equations of state parameters including lattice constant, linear thermal expansion coefficient, and isothermal bulk modulus are calculated and compared with the available experimental data and the latest theoretical results. At an extended pressure and temperature range, P-V-T relationship, lattice constant, and linear thermal expansion coefficient have been predicted. The structural and thermodynamic properties of ZnO with rock-salt structure are summarized in the pressure 0-100 GPa ranges and the temperature up to 3100 K.     

CO2-broadening coefficients in the ν4 + ν5 band of acetylene

The CO₂-broadening coefficients of 24 P- and R-branch transitions in the ν₄ + ν₅ band of acetylene were measured at room temperature using a diode-laser spectrometer. These lines with J values up to 26, were located in the spectral range 1270 to 1400 cm⁻¹. The collisional broadening coefficients were retrieved by fitting the experimental profiles to the Voigt, Rautian, and Galatry lineshape models. Two experimental values for the narrowing coefficient were determined from the spectra and compared with the theoretical narrowing coefficient. The calculations of these broadenings were also performed in the frame of a semiclassical formalism involving a simple intermolecular potential with an adjustable parameter. The theoretical results are in good agreement with the experimental results and reproduce well the J dependence of the broadening coefficients.     

The fundamental band ν2 of D2CO

The ν₂ band of D₂¹³CO in the region of 1570-1760 cm⁻¹ has been analyzed with high accuracy. The limits of the quantum numbers J and K_a are 50 and 16, respectively. The number of the assigned transitions is 3858. A local anharmonic resonance ν₂/2ν₄ at K_a =  8-12 was observed. The Watson’s A-reduced Hamiltonian and anharmonic resonance term were fitted to the observed transitions. The fit resulted in the band center and rotational parameters of the ν₂ band as well as the effective parameters for the 2ν₄ band and anharmonic resonance parameter. The rms deviation of the transitions in the ν₂ band was 0.000364 cm⁻¹.     

Multispectrum analysis of the ν9 band of C2H6: Positions, intensities, self- and N2-broadened half-width coefficients

Line positions, intensities, Lorentz self- and N₂-broadened half-width coefficients have been measured for ^PQ₃, ^PQ₂, ^PQ₁, ^RQ₀, ^RQ₁, ^RQ₂, and ^RQ₃ sub-band transitions in the ν₉ fundamental band of ¹²C₂H₆. A multispectrum nonlinear least-squares fitting technique was used to fit up to 17 high-resolution (∼0.00156 cm⁻¹), room temperature absorption spectra of pure (99.99% chemical purity) natural sample of ethane and lean mixtures of the high-purity ethane diluted with N₂. A Bruker IFS 120HR Fourier transform spectrometer located at the Pacific Northwest National Laboratory (PNNL), in Richland, Washington was used to record the data. A standard Voigt line shape was assumed to fit all the data since no line mixing or other non Voigt line shapes were required to fit any of the spectra used in the analysis. Short spectral intervals (∼2-2.5 cm⁻¹) of all 17 spectra covering a specific ^PQ or ^RQ sub-band were fit simultaneously. For the first time in an ethane band, pressure-broadened half-width coefficients were determined for the torsional-split components. However, for better reliability of the retrieved coefficients for the weaker components (transitions with large intensity ratios of 4:1 or 3:1 for most K levels between the strong and weak components), constraints were used such that the half-width coefficients of both torsional-split components for a given J were identical for a specific broadening gas. No pressure-induced shift coefficients were necessary to fit the spectra to their noise level. The present study revealed for the first time the dependence of self- and N₂-broadened half-width coefficients upon the J, K quantum numbers of the transitions in ethane. A number of transitions belonging to the ν₉+ν₄−ν₄ and the ν₉+2ν₄−2ν₄ hot bands were also observed in the fitted regions and measurements were made when possible.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Optical and electrical properties of thermally evaporated In49Se48Sn3 films

Nearly stoichiometric thin films of In₄₉Se₄₈Sn₃ were deposited at room temperature, by conventional thermal evaporation of the presynthesized materials, onto precleaned glass substrates. The microstructural studies on the as-deposited and annealed films, using transmission electron microscopy and diffraction (TEMD), revealed that the as-deposited films are amorphous in nature, while those annealed at 498 K are crystalline. The optical properties of the investigated films were determined from the transmittance and reflectance data, in the spectral range 650-2500 nm. An analysis of the optical absorption spectra revealed a non-direct energy gap characterizing the amorphous films, while both allowed and forbidden direct energy gaps characterized the crystalline films. The electrical resistance of the deposited films was carried out during heating and cooling cycles in the temperature range 300-600 K. The results show an irreproducible behavior, while after crystallization the results become reproducible. The analysis of the temperature dependence of the resistance (ln(R) vs. 1000/T) for crystalline films shows two straight lines corresponding to both extrinsic and intrinsic conduction. The room temperature I-V characteristics of the as-deposited films sandwiched between similar Ag metal electrodes shows an ohmic behavior, while non-ohmic behavior attributed to space charge limited conduction has been observed when the films are sandwiched between dissimilar Ag/Al metal electrodes.     

Luminescence and diffuse reflectance studies of biacetyl included within p-tert-butylcalixarenes

Powdered solid samples of biacetyl within p-tert-butylcalix[4]arene and p-tert-butylcalix[6]arene were studied with the use of diffuse reflectance techniques to observe the formation of inclusion complexes of the diketone (probe) and those solid powdered matrixes.In all substrates, room temperature phosphorescence was obtained in air equilibrated samples. The decay times vary greatly and the largest lifetime was obtained for biacetyl/p-tert-butylcalix[4]arene, showing that this host cavity well accommodates biacetyl, this way promoting a significant increase of the triplet emission lifetimes of the diketone.Transient absorption spectra of inclusion complexes show the triplet-triplet absorption of biacetyl in the calix[4]arene case, while the ketyl radical formation is observed in the calix[6]arene case.A lifetime distribution analysis has shown a single band, peaking at 1.9 ms for biacetyl/calix[4]arene indicating a unique emissive species and in accordance with an endo inclusion of the probe within the non-polar cavity of the calixarene. Furthermore, in the calix[6]arene inclusion, the lifetime distribution exhibits two maxima peaking at 40 and 174 μs, showing that in this case the probe is emitting in two different environments, a more confined one within the non-polar cavity of the calixarene, while some others probe molecules emit from a location within the polar lower rim, in accordance with an exo-calix complex formation.     

Photodissociation of a HCl molecule adsorbed on ice at T = 210 K

This theoretical work concerns the study of the photodissociation of a HCl molecule adsorbed on an ice surface at T = 210 K. Temperature induced disorder is taken into account by a statistics over several configurations extracted from a classical molecular dynamics (MD) simulation. For each configuration, 3D quantum dynamics of the hydrogen photofragment is investigated using the multi-configuration time-dependent Hartree (MCTDH) method. The absorption spectrum at 210 K is obtained by an average over the spectra calculated for each configuration. The surface disorder results in a smoothing of the interferences structures that appear for some given orientations of HCl depending on the surrounding water molecules orientations.     

Modifications in structural and optical properties of Mn-ion implanted CdS thin films

In this paper, we report on modifications in structural and optical properties of CdS thin films due to 190 keV Mn-ion implantation at 573 K. Mn-ion implantation induces disorder in the lattice, but does not lead to the formation of any secondary phase, either in the form of metallic clusters or impurity complexes. The optical band gap was found to decrease with increasing ion fluence. This is explained on the basis of band tailing due to the creation of localized energy states generated by structural disorder. Enhancement in the Raman scattering intensity has been attributed to the enhancement in the surface roughness due to increasing ion fluence. Mn-doped samples exhibit a new band in their photoluminescence spectra at 2.22 eV, which originates from the d-d (⁴T₁ → ⁶A₁) transition of tetrahedrally coordinated Mn²⁺ ions.     

Growth and spectral characterization of β-Ga2O3 single crystals

Beta gallium oxide (β-Ga₂O₃) single crystals were grown by the floating zone technique. The absorption spectra and the luminescence of the crystals were measured. The absorption spectra showed an intrinsic short cutoff edge around 260 nm with two shoulders at 270 and 300 nm. Not only the characteristic UV (395 nm), blue (471 nm) and green (559 nm) lights, but also the red (692 nm) light can be seen in the emission spectra. The deep UV light was attributed to the existing of quantum wells above the valence band and the red light was owed to the electron-hole recombination via the vicinity donors and acceptors.     

Dicke-narrowed spectral line shapes of CO in Ar: Experimental results and a revised interpretation

The shapes of Dicke-narrowed spectral lines in the fundamental P-branch of CO in Ar are studied by comparing high-resolution measurements and theoretical calculations. The measured spectra were recorded at temperatures between 214 and 324 K, and at pressures between 0.025 and 1 atm. The calculations are based on solving a transport/relaxation equation for the appropriate off-diagonal element of the density matrix; they use a realistic intermolecular potential to determine the speed-dependent collisional broadening, and a rigid sphere potential to determine the Dicke narrowing. It is found that the calculations can reproduce the measured spectra within the experimental noise under all conditions, but that the magnitude of the Dicke narrowing in the measured spectra is 70-90% less than predicted from the mass diffusion constant. A revised view of the collision operator resolves the discrepancy in principle, and leads to a better understanding of the line shape problem in general.