Vapor-phase fluorescence spectra from the second excited singlet state of pyrene and its derivatives

Vapor-phase fluorescence spectra have been measured for pyrene and its simple derivatives, i.e., pyrene-d₁₀, 1-methylpyrene, and 4-methylpyrene. Each of these derivatives shows a weak fluorescence emission which is similar to the fluorescence from the second excited singlet state (S₂) of pyrene and is to be assigned to the S₂-fluorescence. The methyl substitution causes frequency shifts (Δν) in both absorption and fluorescence, and the Δν values for absorption and fluorescence transitions that are associated with the same excited state, i.e., the first excited singlet state (S₁) or the second excited singlet state (S₂), are approximately equal to each other. When the excitation energy increases, the S₂-fluorescence shifts gradually to the red in almost the same way as the S₁-fluorescence. The S₂-fluorescence spectrum has a sort of mirror-image relation to the S₂-absorption. A comparison of S₂-emissions of pyrene and pyrene-d₁₀ suggests that the ratio between the quantum yields of S₂- and S₁-fluorescence may be related to a ratio $\text{?}{}_2\text{?}{}_1$, where ?₁ and ?₂ are the densities of vibrational states in S₁ and S₂ at the energy of excitation.     

Theoretical investigation on photovoltaic properties of PC61BM‐PDPP5T system as a promising polymer‐based solar cell

In the current work, dependent density functional theory and time‐dependent density functional theory calculations coupled with the inherent charge hopping model and some visualization techniques have been used to systematically investigate the photovoltaic properties of PC₆₁BM‐PDPP5T system. Calculations show that PC₆₁BM‐PDPP5T system possesses the relatively large open‐circuit voltage 0.82 V the middle‐sized exciton binding energy (0.690 eV), the small internal reorganization energy (0.159 eV) in the exciton‐dissociation process, but the relatively large one (0.396 eV) in the case of charge‐recombination. With a simplified molecular model, the exciton‐dissociation rate constant, k_dis, is estimated to be as large as 1.156 × 10¹⁰ s^?1 in PC₆₁BM‐PDPP5T phase interface, while the charge‐recombination one, k_rec, is only 1.018 × 10⁷ s^?1 under the same condition, which indicates a rapid and efficient photoinduced exciton‐dissociation process. Copyright © 2016 John Wiley & Sons, Ltd.     

Pressure dependent optical absorption edge shift and compressibility of CdCr2Se4 single crystals

The pressure shift of the optical absorption edge (dE_g/dp = (1.1 ± 0.1) × 10^?6 eV bar^?1) and the compressibility (κ = (1.3 ± 0.) × 10^?6 bar^?1) of single crystalline CdCr₂Se₄ have been measured at ambient temperature. These data suggest an interpretation of the fundamental absorption in terms of either p → p interband or p → localized d charge transfer transitions, but exclude excitations involving s-band states.     

Use of smoke samples in diamond-anvil cells to measure pressure dependence of optical spectra: Application to the ZnO exciton

We present measurements of ZnO exciton peak energies, E₀, at pressures up to 107.3 kbar. Smoke samples consisting of randomly oriented single crystal particles were prepared by oxidizing metallic zinc in air and were collected on one diamond face of a Merrill-Bassett pressure cell. Pressures were measured by the ruby fluorescence technique. In the pressure range between 5 and 90 kbar, our results indicate a consistent linear dependence with dE₀/dP = 2.33 × 10^?3 eV kbar^?1 for both increasing and decreasing pressures. A mixed phase structure is suggested by the observed irregular peak shapes and measured pressure dependence for the sample that had been taken beyond ? 90 kbar where the transformation to the NaCl structure has been reported.     

Charge exchange and excitation cross sections at collisions of alpha particles with be-like impurity oxygen ions in a plasma

The charge exchange and excitation cross sections at collisions of alphas with O⁴⁺(1s ²2s ²) impurity atoms in a hot plasma for striking energies E _c varying from 20 keV to 2 MeV are determined for the first time. The cross sections are calculated using the method of close-coupling equations with 13 singlet four-electron quasi-molecular states taken as a basis. The partial cross sections of charge transfer to the 1s, 2s, and 2p states of a He⁺ ion and for O⁴⁺(1s ²2s ²) → O⁴⁺(1s ²2lnl’) (n = 2, 3) electronic excitation of an oxygen ion are found. The maximal value of the charge exchange total cross section roughly equals 2.2 × 10^?16 cm² at E _c ≈ 0.7 MeV. The excitation total cross section has a maximum of ≈ 7.7 × 10^?16 cm² at E _c ≈ 80 keV for single-electron excitation and ≈6.5 × 10^?16 cm² at E _c ≈ 0.7 MeV for two-electron excitation.     

Screening of exciton states by quasi-two-dimensional electron gas in quantum wells

Changes in the binding energy and oscillator strength of an exciton state due to screening by a quasi-two-dimensional electron gas were calculated self-consistently in a nonlinear approximation. It was shown that the collapse of the bound state proceeds at very small concentrations N _s ?5×10⁹ cm^?2, which is a consequence of taking into account the nonlinearity of the system response to the Coulomb perturbation.     

Channels of radiative recombination and phase transitions in a system of nonequilibrium carriers in a Si0.93Ge0.07/Si thin quantum well

The “exciton gas-plasma” transition (the Mott transition) in a Si_0.93Ge_0.07/Si thin quantum well is investigated using low-temperature photoluminescence. It is demonstrated that this transition is smooth and occurs in the concentration range from approximately 6 × 10¹⁰ to 1.2 × 10¹² cm^?2. At a temperature of 23 K and excitation densities of higher than 10 W/cm², the shape and location of the luminescence line associated with the electron-hole plasma remain unchanged with an increase in the pump density. This can indicate the occurrence of an “electron-hole gas-liquid” transition. It is shown that, in the spectrum of the quantum well, the luminescence of boron-bound excitons dominates at liquid-helium temperatures and low excitation densities, whereas the free-exciton luminescence dominates at temperatures above 10 K. The influence of the homogeneous and inhomogeneous broadening on the electron-hole plasma and exciton luminescence is discussed.     

Fluorescence quantum yield of carbon dioxide for quantitative UV laser-induced fluorescence in high-pressure flames

The fluorescence quantum yield for ultraviolet laser-induced fluorescence of CO₂ is determined for selected excitation wavelengths in the range 215–250 nm. Wavelength-resolved laser-induced fluorescence (LIF) spectra of CO₂, NO, and O₂ are measured in the burned gases of a laminar CH₄/air flame (φ=0.9 and 1.1) at 20 bar with additional NO seeded into the flow. The fluorescence spectra are fit to determine the relative contribution of the three species to infer an estimate of fluorescence quantum yield for CO₂ that ranges from 2–8×10^?6 depending on temperature and excitation wavelength with an estimated uncertainty of ±0.5×10^?6. The CO₂ fluorescence signal increases linearly with gas pressure for flames with constant CO₂ mole fraction for the 10 to 60 bar range, indicating that collisional quenching is not an important contributor to the CO₂ fluorescence quantum yield. Spectral simulation calculations are used to choose two wavelengths for excitation of CO₂, 239.34 and 242.14 nm, which minimize interference from LIF of NO and O₂. Quantitative LIF images of CO₂ are demonstrated using these two excitation wavelengths and the measured fluorescence quantum yield.     

Fluorescence quenching of vaporous polycyclic aromatic hydrocarbons by oxygen

The fluorescence quenching by oxygen of vapors of nine polycyclic aromatic hydrocarbons with strongly different oxidation potentials 0.44 eV < E _ox < 1.61 eV (anthracene, 9-methylanthracene, 2-aminoanthracene, 9,10-dibromanthracene, pyrene, chrysene, phenanthrene, fluoranthene, and carbazole) is studied. From the dependences of the fluorescence decay rates and intensities on the oxygen pressure P _O2, the quenching rate constants k _S ^O2 for the excited singlet states S ₁ and the fraction f _S ^O2 of the S ₁ states quenched by oxygen are estimated. At P _O2 = 5 Torr, the k _S ^O2 constants vary from 1.2 × 10⁷ to 3.0 × 10⁵ s^?1 Torr^?1, while the fraction of the quenched excited singlet states changes from 0.1 (fluoranthene) to 0.7 (chrysene) and 0.8 (pyrene). The dependences of k _S ^O2 on the photophysical and electron-donor characteristics of the fluorescing compounds are analyzed. It is shown that, in the gas phase of anthracene and its derivatives, the magnitudes of k _S ^O2 are limited by the rate constants of gas-kinetic collisions k _gk and do not depend on the electron-donor characteristics of fluorophores, while the fraction of quenched states f _S ^O2 changes with the oxidation potential. For compounds with k _S ^O2 < k gk, both the rate constants k _S ^O2 and the fraction of quenched states f _S ^O2 depend on the E _ox of sensitizers, which demonstrates an important role played by the charge-transfer interactions in quenching of the S ₁ states. The dependence of the rate constants k _S ^O2 on the free energy of electron transfer ΔG _et is considered.     

Mechanistic Insights into the Inhibition of Endo-β 1,4 Xyloglucan Hydrolase by a Classical Aspartic Protease Inhibitor

This is the first report of inactivation of xyloglucanase from Thermomonospora sp by pepstatin A, a specific inhibitor towards aspartic proteases. The steady state kinetics revealed a reversible, competitive, two-step inhibition mechanism with IC ₅₀ and K _i values of 3.5?±?0.5 μM and 1.25?±?0.5 μM respectively. The rate constants determined for the isomerization of EI to EI^* and the dissociation of EI* were 14.5?±?1.5?×?10^?5?s^?1 and 2.85?±?1.2?×?10^?8?s^?1 respectively, whereas the overall inhibition constant K _i ^* was 27?±?1 nM. The conformational changes induced upon inhibitor binding to xyloglucanase were monitored by fluorescence analysis and the rate constants derived were in agreement with the kinetic data. The abolished isoindole fluorescence of o-phthalaldehyde (OPTA)-labeled xyloglucanase and far UV analysis suggested that pepstatin binds to the active site of the enzyme. Our results revealed that the inactivation of xyloglucanase is due to the interference in the electronic microenvironment and disruption of the hydrogen-bonding network between the essential histidine and other residues involved in catalysis.     

Pulsed dephotolysis in emulsion nanocrystals of silver halides: I. Recombination processes at early stages of photolysis

Early stages of formation of few-atom clusters of photolytic silver in AgBr nanocrystals are studied using the pulsed dephotolysis technique. It is shown that dephotolysis is characterized by a clearly pronounced dependence on the pulse duration of nonactinic and actinic radiations, the highest efficiency of dephotolysis being achieved for nanosecond pulses. The rate constant of recombination of free electrons with captured holes is determined (κ_p = (6 ± 1) × 10^?9 cm³ s^?1) and the dependence of the recombination rate on the level of excitation is found. The maximum recombination rate for the highest excitation level is found to be V _p ^max = 10⁹ s^?1 and the surface concentration of recombination centers is determined to be N _r = (2 ± 0.5) × 10¹¹ cm^?2.     

Spectral characteristics and fluorescence quenching of N,N′-bis(4-pyridyl)-3,4:9,10-perylenebis(dicarboximide) (BPPD)

The photophysical properties such as electronic absorption, molar absorptivity, emission spectra, fluorescence quantum yield and fluorescence lifetime of N,N′-bis(4-pyridyl)-3,4:9,10-perylene bis(dicarboximide) (BPPD) have been measured in different solvents. Both electronic absorption and fluorescence spectra are not sensitive to medium polarity, while the fluorescence quantum yield (?_f) is solvent dependent. The ground state geometry has been computed by using density functional theory (DFT), the transition from HOMO to LUMO from perylene core with maximum absorption at 512 nm and HOMO–LUMO energy difference equal 2.53 eV. BPPD dye undergoes molecular aggregation to dimmer or higher aggregates in dimethyl sulfoxide (DMSO). Crystalline solids of BPPD gives excimer-like emission at 676 nm. The fluorescence quenching of BPPD is also studied using hydrated ferric oxide nanoparticle (FeOOH), and the Stern–Volmer rate constants (K_sv) were calculated as 8×10⁶ and 9.2×10⁶ M^?1 in ethanol and ethylene glycol, respectively.     

Oxygen Diffusion into Multiwalled Carbon Nanotube Doped Polystrene Latex Films Using Fluorescence Technique

This study examines the oxygen diffusion into polystyrene (PS) latex/multiwalled carbon nanotube (MWNT) nanocomposite films (PS/MWNT) consisting of various amounts of MWNT via steady state fluorescence technique (SSF). PS/MWNT films were prepared from the mixture of MWNT and pyrene (P)-labeled PS latexes at various compositions at room temperature. These films were then annealed at 170 °C above glass transition (T_g) temperature of PS. Fluorescence quenching measurements were performed for each film separately to evaluate the effect of MWNT content on oxygen diffusion. The Stern-Volmer equation for fluorescence quenching is combined with Fick’s law for diffusion to derive the mathematical expressions. Diffusion coefficients (D) were produced and found to be increased from 1.1?×?10^?12 to 41?×?10^?12 cm²s^?1 with increasing MWNT content. This increase was explained via the existence of large amounts of pores in composite films which facilitate oxygen penetration into the structure.     

Ferroelectric and optical properties of Ba6Ti2Nb8O30 single crystals

The dielectric, optical and non-linear optical properties of Ba₆Ti₂Nb₈O₃₀ single crystals were examined from room temperature up to the Curie temperature of 245°C. The spontaneous polarization at room temperature was estimated as 0·22±0·01 C/m². The linear electrooptic constants were measured as r₃₃^T=(1·17±0·02)×10^?10 and r₁₃^T=(0·42±0·01)×10^?10 m/V. The non-linear optical coefficients were d₃₃=(15·1±2·0)×10^?12 and d₃₁=(11·0±2·0)×10^?12 m/V, which are comparable to those of Ba₄Na₂Nb₁₀O₃₀. Temperature dependences of δ₃₃ and δ₃₁ (Miller's δ) were found to be proportional to that of P_s.     

Absorption of Dy3+ and Nd3+ ions in BaR 2F8 single crystals

The Dy³⁺ absorption and excitation spectra of BaY₂F₈ and BaYb₂F₈ single crystals are investigated in the ultraviolet, vacuum ultraviolet, and visible ranges at a temperature of 300 K. These crystals exhibit intense broad absorption bands due to the spin-allowed 4f-5d transitions in the range (56–78) × 10^?3 cm^?1 and less intense absorption bands that correspond to the spin-forbidden transitions in the range (50–56) × 10^?3 cm^?1. The Nd³⁺ absorption spectra of BaY₂F₈ single crystals are studied in the range (34–82) × 10^?3 cm^?1 at 300 K for different crystal orientations.     

Quenching of ππ* triplet states of vaporous polycyclic aromatic compounds by oxygen

The oxygen quenching rate constants k _T ^O2 of the triplet state T ₁ of vapors of polycyclic aromatic hydrocarbons (PAHs) with strongly different oxidation potentials 0.44 eV < E _OX < 1.61 eV and energies of the triplet levels 14800 cm^?1 < E _T < 24500 cm^?1 (anthracene, 2-aminoanthracene, 9-nitroanthracene, chrysene, phenanthrene, fluoranthene, and carbazole) are estimated from the measured dependences of the decay rates and intensities of delayed fluorescence on the oxygen pressure P _O2. It is found that the rate constants k _T ^O2 vary from 4 × 10³ (9-nitroanthracene) to 4 × 10⁵ s^?1 Torr^?1 (2-aminoanthracene) and increase with decreasing oxidation potentials E _OX of PAHs. The rate constants k _T ^O2 for vapors and solutions are compared. The dependences of k _T ^O2 on the free energy of two intermolecular processes, namely, triplet energy transfer to oxygen and electron transfer, are analyzed. It is shown that the rate constants k _T ^O2 increase with decreasing electron transfer free energy, which proves that, along with energy transfer, charge-transfer interactions contribute to the quenching of the triplet states of PAH vapors.     

Time constants of radiative transitions from the 5<Emphasis Type="Italic">d</Emphasis>[3/2]<Subscript>1</Subscript> level of a xenon atom

Integral yields of spontaneous emission at wavelengths of 1.73, 2.03, and 2.65 μm have been measured upon excitation of pure xenon by a pulsed electron beam. These yields have been analyzed and experimental data have been obtained on time constants of radiative transitions 5d[3/2]₁ → 6p[5/2]₂, 5d[3/2]₁ → 6p[3/2]₁, and 5d[3/2]₁ → 6p[1/2]₀ of XeI, which appeared to be equal to (2300 ± 400) × 10^?9, (300 ± 40) × 10^?9, and (1300 ± 200) × 10^?9 s, respectively. It is shown that the experimental data are in a qualitative agreement with the results of computational and theoretical investigations. The results of averaging the experimental and calculated data are proposed for use as recommended values of the corresponding constants.     

Measurement of Ar(I) and Ar(II) transition probabilities in LTE ARC plasmas

The transition probabilities of two Ar(I) lines and one Ar(II) line have been measured in emission on wall-stabilized argon arc plasmas (0·5×10⁵?p, Nm^-2?3×10⁵; 10,000?T, K?20,000; 10²²?N_e, m^-3?5×10²³) using the “method of best fit (MBF)”. The results (without line-wing correction) are for Ar(I) at 714·7 nm, A_nm=5·66×10⁵ s^-1±5%; for Ar(I) at 430·0 nm, A_nm=3·40×10⁵ s^-1±5%; for Ar(II) at 480·6 nm, A_nm=8·82×10⁷ s^-1±7%. These values were not influenced by deviations from LTE, which have been observed at electron number densities n_e?10²³ m^-3. The small uncertainties were achieved after careful corrections of different sources of error.     

Energy transfer across an anthracene-gold interface

From the fluorescence excitation spectrum the rate b_ET at which anthracene singlet excitons are quenched at a gold layer is determined. The distance between the anthracene crystal surface and the metal layer is varied by means of fatty acid monolayer assemblies. The b_ET is found to follow a d^-3-law, the proportionality constant being β = (10.3 ± 2.0) × 10^-18 cm³. This confirms the applicability of the theory by Chance et al. predicting b_ET = 12.7 × 10^-18d^-3.     

Fluorescence lifetimes and radiative rate constants of alkanes at 25°C

Fluorescence lifetimes of 33 alkanes were measured at 25°C using a 0.7 ns pulse radiolysis system and the relationship between molecular structure, fluorescence lifetime (τ), quantum yield (Φ_f) and radiative rate constant (R = $\text{Φ}{}_{\mathrm{f}}\text{τ}$) is discussed. The τ's showed a large dependence on the molecular structure, however, the R-values were approximately constant for groups of alkanes: R = 1.3×10⁶s^?1 for n-alkanes, R ≈ 4×10⁶ s^?1 for aliphatic vicinally substituted dimethyl alkanes, R = 7×10⁶s^-1 for cyclohexane and alkylcyclohexanes, and R = 10×10⁶s^?1 for di- and trimethylcyclohexanes. The excited state lifetimes of some non-fluorescing alkanes were also determined from steady-state photolytic quenching data and found to be very low (? 0.3 ns).