Photophysical properties, laser activity and photoreactivity of a heteroaryl chalcone: A model of solvatochromic fluorophore

The absorption and fluorescence characteristics of 3-(4′-dimethylaminophenyl)-1-(2-thienyl)prop-2-en-1-one (DMATP) have been investigated in different solvents. DMATP dye exhibits a large red shift in both absorption and emission spectra as solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation due to an intramolecular charge transfer interaction. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. A crystalline solid of DMATP gave an excimer like emission at 570 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. A dye solution ca. 10⁻³ mol dm⁻³ in CHCl₃ gave a good laser emission in the range 480–560 nm with emission maximum at 530 nm upon pumping by nitrogen laser (λ_ex=337.1 nm). The excitation energy transfer from 7-dimethylamino-4-methyl coumarine (DMC) to DMATP has been also studied in CHCl₃ and the values of energy transfer rate constant and critical transfer distance indicate a Főrster-type mechanism. The photoreactivity and net photochemical quantum yield of DMATP in chloromethane solvents are also determined. We applied semiempirical MO calculation using AMI and ZINO/S calculation to understand the geometric and electronic structure of DMATP molecule in both ground and excited states.     

Spectral characterization and energy levels of Cr:Sc2(MoO4)3 crystal

This paper reports the spectral properties and energy levels of Cr³⁺:Sc₂(MoO₄)₃ crystal. The crystal field strength Dq, Racah parameter B and C were calculated to be 1408 cm⁻¹, 608 cm⁻¹ and 3054 cm⁻¹, respectively. The absorption cross sections σ_α of ⁴A₂→⁴T₁ and ⁴A₂→⁴T₂ transitions were 3.74×10⁻¹⁹ cm² at 499 nm and 3.21×10⁻¹⁹ cm² at 710 nm, respectively. The emission cross section σ_e was 375×10⁻²⁰ cm² at 880 nm. Cr³⁺:Sc₂(MoO₄)₃ crystal has a broad emission band with a broad FWHM of 176 nm (2179 cm⁻¹). Therefore, Cr³⁺:Sc₂(MoO₄)₃ crystal may be regarded as a potential tunable laser gain medium.     

Compositionally asymmetrical multiquantum wells: “Pseudo-molecules” for giant optical nonlinearities in the infrared (9–11 μm)

Intersubband transitions in quantum well have extremely large oscillator strengths and induce strong nonlinear effects in structures where inversion symmetry is broken, realized by growing AlGaAs quantum wells with asymmetrical A1 gradients. These compositionally asymmetrical multiquantum wells may thus be viewed as giant “quasimolecules” optimized for optimal nonlinearities in the mid infrared. Optical rectification as well as second harmonic generation have been measured in those structures using a continuous CO₂ laser. At 10.6 μm the nonlinear coefficients are more than 3 orders of magnitude higher in these samples than for bulk GaAs (i.e. χ₀⁽²⁾ = 5.3 × 10⁻⁶m/V, χ_2ω⁽²⁾ = 7.2 × 10⁻⁷ m/V) and are in good agreement with theoretical predictions. We present more complex “pseudo-molecules” involving weakly coupled quantum wells. The optical rectification effects in these devices are so large χ₀⁽²⁾ = 1.6 × 10⁻³ m/V) that application to infrared detection may be envisioned.     

NOx generation in laser-produced plasma in air as a function of dissipated energy

An experimental study on the production of NO_x as a function of dissipated energy in laser-produced plasma in air is presented. A plasma was produced by focusing a (60–180) mJ, 5 ns, 532 nm pulse from a Q-switched Nd:YAG laser. The results show that for laser energy in the range of 13–99 mJ the laser plasma generates 6.7×10¹⁶ NO_x molecules per joule and 4.6×10¹⁶ NO molecules per joule. An order of magnitude estimate of the NO and NO_x production per unit volume of heated gas based on a simple model show that the NO_x and NO production efficiency in air are about 3×10²² and 2×10²² molecules J⁻¹ m⁻³.     

Elementary reactions of formyl (HCO) radical studied by laser photolysis—transient absorption spectroscopy

Several elementary reactions of formyl radical of combustion importance were studied using pulsed laser photolysis coupled to transient UV–Vis absorption spectroscopy: HCO → H + CO (1), HCO + HCO → products (2), and HCO + CH₃ → products (3). One-pass UV absorption, multi-pass UV absorption as well as cavity ring-down spectroscopy in the red spectral region were used to monitor temporal profiles of HCO radical. Reaction (1) was studied over the buffer gas (He) pressure range 0.8–100 bar and the temperature range 498–769 K. Reactions (2a), (2b), (2c), (3a) and (3b) as well as the UV absorption spectrum of HCO, were studied at 298 and 588 K, and the buffer gas (He) pressure of 1 bar. Pulsed laser photolysis (308, 320, and 193 nm) of acetaldehyde, propionaldehyde, and acetone was used to prepare mixtures of free radicals. The second-order rate constant of reaction (1) obtained from the data at 1 bar is: k₁(He) = (0.8 ± 0.4) × 10⁻¹⁰exp(−(66.0 ± 3.4) kJ mol⁻¹/RT) cm³ molecule⁻¹ s⁻¹. The HCO dissociation rate constants measured in this work are lower than those reported in the previous direct work. The difference is a factor of 2.2 at the highest temperature of the experiments and a factor of 3.5 at the low end. The experimental data indicate pressure dependence of the rate constant of dissociation of formyl radical 1, which was attributed to the early pressure fall-off expected based on the theory of isolated resonances. The UV absorption spectrum of HCO was revised. The maximum absorption cross-section of HCO is (7.3 ± 1.2) × 10⁻¹⁸ cm² molecule⁻¹ at 230 nm (temperature independent within the experimental error). The measured rate constants for reactions (2a), (2b), (2c), (3a) and (3b) are: k₂ = (3.6 ± 0.8) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ (298 K); k₃ = (9.3 ± 2.3) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹(298 and 588 K).     

Study on nonlinear optical absorption properties of [(CH3)4N]2[Cu(dmit)2] by Z-scan technique

The third-order optical nonlinearities of an organo-metallic compound, [(CH₃)₄N]₂[Cu(dmit)₂] (dmit²⁻=4,5-dithiolate-1,3-dithiole-2-thione), abbreviated as MeCu, dissolved in acetone are characterized by Z-scan technique with picosecond and nanosecond laser pulses in the near-infrared region. Two-photon absorption has been found when the sample solution is irradiated by 40 ps pulse width at 1064 nm and the two-photon absorption (TPA) coefficient β_TPA is 4×10⁻¹³ m/W. While excited by 15 ns laser pulses at 1053 nm, the Z-scan spectra reveal strong reverse saturable absorption (RSA) and the nonlinear absorption coefficient β_RSA is estimated to be as high as 7.07×10⁻¹¹ m/W which is much larger than β_TPA. An explanation for this enhancement is given. All the results suggest that MeCu may be a promising candidate for the application to optical limiting in the near-infrared region.     

Rotational absorption spectrum of methylene fluoride in the 20–100 cm region

The pure rotational spectrum of CH₂F₂ was recorded in the 20–100 cm⁻¹ spectral range and analyzed to obtain rotation and centrifugal distortion constants. Analysis of the data yielded rotation constants: A = 1.6392173 ± 0.0000015, B = 0.3537342 ± 0.00000033, C = 0.3085387 ± 0.00000027, τ_aaaa = −(7.64 ± 0.46) × 10⁻⁵, τ_bbbb = −(2.076 ± 0.016) × 10⁻⁶, τ_cccc = −(9.29 ± 0.12) × 10⁻⁷, T₁ = (4.89 ± 0.20) × 10⁻⁶, and T₂ = −(1.281 ± 0.016) × 10⁻⁶cm⁻¹.     

Influence of oxygen growth pressure on laser ablated Cr-doped In2O3 thin films

We present a systematic investigation of the effects of oxygen growth pressure on the structural, optical, and electrical properties of In₂O₃:Cr thin films grown by pulsed laser deposition. X-ray diffraction analysis showed increases in lattice constant from 10.103 Å to 10.337 Å, and in particle size from 13.9 nm to 35.5 nm as the oxygen growth pressure increased from 7.5 × 10⁻⁶ Torr to 7.5 × 10⁻³ Torr, respectively. The observed shift in the X-ray diffraction peaks to lower angles was assumed to be caused by the reduction in the lattice defect density, precisely oxygen vacancies. The optical transparency increased with partial oxygen pressure (P_O2), and an average transmittance of 85% was obtained at 7.5 × 10⁻³ Torr. The films are highly conducting with resistivity as low as 2 × 10⁻⁴ Ω cm and mobility as high as 133 cm/V s. Temperature dependent resistivity measurements in the 45 < T < 300 K temperature range reveal that films grown at 7.5×10⁻⁶≤P_O2≤7.5×10⁻⁴ Torr exhibit negative temperature coefficient of resistivity (TCR) below approximately T = 60 K, T = 120 K, T = 160 K; then positive TCR in the temperature intervals 60 < T < 300 K, 120 < T < 300 K, and 160 < T < 300 K, respectively. This suggests that two disparate mechanisms govern electrical dc transport in the two temperature regions. Film grown at P_O2 of 7.5 × 10⁻³ Torr displayed typical semiconducting behavior with negative TCR in the whole temperature region.     

Polarization spectroscopy of ion-pair states of ICl

Molecular constants for the E0⁺(³P₂) and 1(³P₂) ion-pair states of ICl vapor have been determined using sequential two-photon polarization-labeling spectroscopy. The two states are coupled by a heterogeneous perturbation which is analyzed in some detail for low-lying vibrational levels of 1(³P₂). The I³⁵Cl potential constants for the 1(³P₂) state and the rotation-vibration constants for the set of f sublevels—i.e., the constants unaffected by coupling with the E state—are (in cm⁻¹) 1(³P₂): Y_0,0= 39103.814(32), Y_1,0= 170.213(15), Y_2,0= −0.4528(22), Y_3,0= −7.0(12) × 10⁻⁴, Y_4,0= −1.48(24) × 10⁻⁵ and Y_5,0= −6.6(19) × 10⁻⁸, Y^(f)_0,1= 5.6878(17) × 10⁻² Y^(f)_1,1= −2.110(24) × 10⁻⁴, Y^(f)_2,1= −1.23(62) × 10⁻⁷, and Y^(f)_0,1= −3.08(22) × 10⁻⁸Likewise, the I³⁵Cl constants determined for the E 0⁺(³P₂) state are E 0⁺(³P₂: Y_0,0= 39054.38(61), Y_1,0= 166.96(10), Y_2,0 = −0.3995(42), Y_0,1= 5.738(31) × 10⁻², and Y_1,1= −1.67(26) × 10⁻⁴Practical constraints in pumping the sequence E 0⁺ ← B 0⁺ ← × 0⁺ restrict the analysis of the E state to levels v = 9–15. Given the long extrapolation to the equilibrium state the 3σ statistical uncertainties quoted for these constants should be treated with caution.     

High Resolution Study of Deuterated Hydrogen Sulfide in the Region 2400-3000 cm

High resolution Fourier transform spectra of deuterated hydrogen sulfide have been recorded in the region 2400-3000 cm⁻¹. Rotational structures of the ν₁ + ν₂, ν₂ + ν₃ bands of D₂³²S, of the ν₃ and ν₁ + ν₂ bands of HD³²S, and of the ν₁ + ν₂ band of HD³⁴S were analyzed. Band centers and rotational, centrifugal distortion, and resonance parameters were obtained, which reproduce the initial values of the upper energy levels within a mean accuracy of 1.39 × 10⁻⁴ cm⁻¹ for the states (110) and (011) of D₂³²S, 1.61 × 10⁻⁴ cm⁻¹ and 1.82 × 10⁻⁴ cm⁻¹ for the states (001) and (110) of HD³²S, and 2.09 × 10⁻⁴ cm⁻¹ for the state (110) of HD³⁴S, respectively.     

Effect of oxygen partial pressure on the structural and optical properties of dc reactive magnetron sputtered molybdenum oxide films

Molybdenum oxide films (MoO₃) were deposited on glass and crystalline silicon substrates by sputtering of molybdenum target under various oxygen partial pressures in the range 8 × 10⁻⁵–8 × 10⁻⁴ mbar and at a fixed substrate temperature of 473 K employing dc magnetron sputtering technique. The influence of oxygen partial pressure on the composition stoichiometry, chemical binding configuration, crystallographic structure and electrical and optical properties was systematically studied. X-ray photoelectron spectra of the films formed at 8 × 10⁻⁵ mbar showed the presence of Mo⁶⁺ and Mo⁵⁺ oxidation states of MoO₃ and MoO_3−x. The films deposited at oxygen partial pressure of 2 × 10⁻⁴ mbar showed Mo⁶⁺ oxidation state indicating the films were nearly stoichiometric. It was also confirmed by the Fourier transform infrared spectroscopic studies. X-ray diffraction studies revealed that the films formed at oxygen partial pressure of 2 × 10⁻⁴ mbar showed the presence of (0 k 0) reflections indicated the layered structure of α-phase MoO₃. The electrical conductivity of the films decreased from 3.6 × 10⁻⁵ to 1.6 × 10⁻⁶ Ω⁻¹ cm⁻¹, the optical band gap of the films increased from 2.93 to 3.26 eV and the refractive index increased from 2.02 to 2.13 with the increase of oxygen partial pressure from 8 × 10⁻⁵ to 8 × 10⁻⁴ mbar, respectively.     

Lasing characteristics of Rhodamine B and Rhodamine 6G as a sensitizer in sol–gel silica

We report lasing characteristics of Rhodamine B (Rh. B) in sol–gel silica under excitation with frequency-doubled Nd:YAG laser and sensitization with Rhodamine 6G (Rh. 6G). The principle of radiative energy transfer (from Rh. 6G to Rh. B) has been utilized as a longitudinally Rh. 6G laser (at 585 nm)-pumped Rh. B laser process in the same sample. Rh. B offers a high photostable and efficient laser dye in sol–gel silica sensitized with Rh. 6G; 75,000 shots as a laser half-lifetime of the sample and 24% efficiency at pumping intensity 0.1 J/cm² of 532 nm. Wavelength shift occurs from 606 to 630 nm in the Rh. B laser with increasing its concentration from 1×10⁻⁴ to 8×10⁻⁴ M. The measured optical gain for Rh. B sensitized with Rh. 6G in sol–gel silica is higher than that in ethanol. A new effect has been observed; at 1×10⁻⁴ M of Rh. B and 0.5×10⁻⁴ M of Rh. 6G mixture, the emitted color of laser is changed by changing the pump intensity of frequency-doubled Nd:YAG laser.     

Exceptional sensitivity to neutrino parameters with a two-baseline Beta-beam set-up

We examine the reach of a Beta-beam experiment with two detectors at carefully chosen baselines for exploring neutrino mass parameters. Locating the source at CERN, the two detectors and baselines are: (a) a 50 kton iron calorimeter (ICAL) at a baseline of around 7150 km which is roughly the magic baseline, e.g., ICAL@INO, and (b) a 50 kton Totally Active Scintillator Detector at a distance of 730 km, e.g., at Gran Sasso. We choose ⁸B and ⁸Li source ions with a boost factor γ of 650 for the magic baseline while for the closer detector we consider ¹⁸Ne and ⁶He ions with a range of Lorentz boosts. We find that the locations of the two detectors complement each other leading to an exceptional high sensitivity. With γ=650 for ⁸B/⁸Li and γ=575 for ¹⁸Ne/⁶He and total luminosity corresponding to 5×(1.1×10¹⁸) and 5×(2.9×10¹⁸) useful ion decays in neutrino and antineutrino modes respectively, we find that the two-detector set-up can probe maximal CP violation and establish the neutrino mass ordering if sin²2θ₁₃ is 1.4×10⁻⁴ and 2.7×10⁻⁴, respectively, or more. The sensitivity reach for sin²2θ₁₃ itself is 5.5×10⁻⁴. With a factor of 10 higher luminosity, the corresponding sin²2θ₁₃ reach of this set-up would be 1.8×10⁻⁵, 4.6×10⁻⁵ and 5.3×10⁻⁵ respectively for the above three performance indicators. CP violation can be discovered for 64% of the possible δ_CP values for sin²2θ₁₃10⁻³ (8×10⁻⁵), for the standard luminosity (10 times enhanced luminosity). Comparable physics performance can be achieved in a set-up where data from CERN to INO@ICAL is combined with that from CERN to the Boulby mine in United Kingdom, a baseline of 1050 km.     

Waveguide and diode heterodyne measurements with CO2 laser and assignment of the CW FIR laser emission of OCS

Heterodyne spectra of carbonyl sulfide have been obtained with saturation in a CO₂ waveguide laser and without saturation with a diode laser. The absolute uncertainties of the measured positions lie between 10⁻⁴ and 7 × 10⁻⁶ cm⁻¹. The CW submillimeter laser line of OCS at 378 μm has been assigned to the J = 65 → 64 transition in the 02²0e state of ¹⁶O¹²C³²S, with a pumping through the R(64) line of 02²0e ← 00⁰0, a Δ-Σ transition weakly allowed by the l-type resonance.     

Collective excitations in low-density 2D electron systems

We report the observation of sharp plasmon and magnetoplasmon modes in ultra-low-density 2D electron systems. Well defined dispersions for the modes are observed at densities as low as 1.1×10⁹ cm⁻² and with excitation wave vectors as large as 1.2×10⁵ cm⁻¹. Interestingly, both modes are found to be more easily measured in low-density systems than in high-density systems. The strength of the light scattering cross-sections at low density suggests potential applications to the study of quantum phase transitions at large r_s.     

Line Intensities in the ν1, ν3, and 2ν2 Bands of H2Se

Using a high-resolution Fourier transform spectrum of hydrogen selenide in natural abundance, about 600 intensities of lines belonging to the ν₁, ν₃, and 2ν₂ bands of H₂⁸⁰Se were measured. A least-squares fit of these intensities was performed, allowing determination of the vibrational transition moments of these bands and their rotational corrections. Finally, the first derivatives of the dipole moment with respect to the normal coordinates q₁ and q₃ were found to be ∂μ_χ/∂q₁ = (−0.5938 ± 0.010) × 10⁻¹ and ∂μ_z/∂q₃ = (0.5683 ± 0.010) × 10⁻¹ Debye, respectively.     

Analysis of the 2ν3 band of CD3F at 5.06 μm recorded under high resolution

The 2ν₃(A₁) band of ¹²CD₃F near 5.06 μm has been recorded with a resolution of 20–24 × 10⁻³ cm⁻¹. The value of the parameter (α^B − α^A) for this band was found to be very small and, therefore, the K structure of the R(J) and P(J) manifolds was unresolved for J < 15 and only partially resolved for larger J values. The band was analyzed using standard techniques and values for the following constants determined: ν₀ = 1977.178(3) cm⁻¹, B″ = 0.68216(9) cm⁻¹, D″_J = 1.10(30) × 10⁻⁶ cm⁻¹, α^B = (B″ − B′) = 3.086(7) × 10⁻³ cm⁻¹, and β^J = (D″_J − D′_J) = −3.24(11) × 10⁻⁷ cm⁻¹. A value of α^A = (A″ − A′) = 2.90(5) × 10⁻³ cm⁻¹ has been obtained through band contour simulations of the R(J) and P(J) multiplets.     

Nonlinear optical properties of Cu nanocluster composite fabricated by 180 keV ion implantation

Metal nanocluster composite glass prepared by 180 keV Cu ions into silica with dose of 5×10¹⁶ ions/cm² has been studied. The microstructural properties of the nanoclusters has been verified by optical absorption spectra and transmission electron microscopy (TEM). Third-order nonlinear optical properties of the nanoclusters were measured at 1064 and 532 nm excitations using Z-scan technique. The nonlinear refraction index, nonlinear absorption coefficient, and the real and imaginary parts of the third-order nonlinear susceptibility were deduced. Results of the investigation of nonlinear refraction by the off-axis Z-scan configuration were presented and the mechanisms responsible for the nonlinear response were discussed. Third-order nonlinear susceptibility χ⁽³⁾ of this kind of sample was determined to be 8.7×10⁻⁸ esu at 532 nm and 6.0×10⁻⁸ esu at 1064 nm, respectively.     

Effects of superstrings in collisions

Superstring theory in d = 10 dimensions after Calabi—Yau compactification yields a minimum low-energy gauge group SU(3)_C × SU(2)_L × U(1)_Y × U(1)_E. The low-energy theory includes particles with the quantum numbers of 27 representations of E₆, each of which contains an extra neutrino ν^c conventionally called a “right-handed neutrino”. The contributions of ν and ν^c to through Z⁰ and Z_E mixing is calculated. Small contributions are found of the new right-handed neutrino and of the superstring boson Z_E to σ(e⁺e⁻ → γ + nothing).     

Large nonlinear optical properties of Fe2O3 nanoparticles

Nonlinear optical properties of Fe₂O₃ nanoparticles were investigated by the signal-beam Z-scan technique with Ar⁺ and Ne–He lasers. The largest reported effective nonlinear coefficient, n₂=−8.07×10⁻⁷ cm²/W, was obtained. It is demonstrated that the nonlinear optical response originals from quantum confinement effect.