Efficient Preparation of D2 Molecules in v=2 by Stimulated Raman Pumping

We report the preparation of D₂ molecules in v=2 level in molecular beam condition. A single longitudinal mode laser system was used for excitation of D₂ from (v=0, j=0) to (v=2, j=0) with the scheme of stimulated Raman pumping. An excitation efficiency of 25.2% has been achieved, which was determined by the scheme of resonance-enhanced multiphoton ionization. Dependence of relative excitation efficiency on laser energy has been measured. We found that the increasing rate of excitation efficiency became slower as pulse energy of Stokes laser increase, while the excitation efficiency still increases approximately linearly with pump pulse energies up to 60 mJ. The spectral line shapes of Raman transition was also measured at different laser energies and considerable dynamical Stark effect was observed. A single peak was found on the three dimension surface of relative excitation efficiency, indicating the process occurred in the present study is a process of stimulated Raman pumping instead of stimulated adiabatic Raman passage.     

Identification of charge transfer (CT) transition in (Gd,Y)BO3:Eu phosphor under 100-300 nm

A broad excitation band in an excitation spectrum of (Gd,Y)BO₃:Eu was observed in the VUV region. It could be considered that this band was composed of two bands at about 160 and 166 nm. The preceding band was assigned to the BO₃ group absorption. The later one at about 166 nm could be assigned to the charge transfer (CT) transition of Gd³⁺-O²⁻. Such an assignment was deduced from the result that broadbands at around 170 nm for GdAlO₃:Eu, and at 183 nm for Gd₂SiO₅:Eu are due to the CT transition of Gd³⁺-O²⁻; this was also identified by CaZr (BO₃)₂:Eu. Since there are no Gd³⁺ ions in it; a weak band in the VUV region in the excitation spectrum of Ca_0.95ZrEu_0.05(BO₃)₂ was observed. The excitation spectra were overlapped between the CT transition of Gd³⁺-O²⁻ and BO₃ group absorption, and it caused the emission of Eu³⁺ effectively in the trivalent europium-doped (Gd,Y)BO₃ host lattice under 147 nm excitation. Intense broad excitation bands were observed at about 155 nm for YBO₃:Eu and at about 153 nm for YAlO₃:Eu; it could be attributed to the CT transition between Y³⁺ and O²⁻. As a result, under the xenon discharge (147 nm) excitation, the intense emission of Eu³⁺ in GdBO₃ was found to be more convenient just because of the partial substitution of Y³⁺ for Gd³⁺.     

Photochemical decay of butynal (H3CCCCHO) in the gas phase following S1(nπ*) ← S0 excitation

After excitation into the S₁(nπ*) ← absorption, butynal decomposes into CO and propyne (H₃CCCH). Emission lifetimes, photoproduct quantum yields, and phosphorescence quantum yields were measured in the pressure range 0.25–2 Torr at room temperature using excitation energies between 26620 (0-0 transition) and 33300 cm^?1. Based on these results and on those of the propynal (HCCCHO) dynamics previously reported. a photodissociation mechanism for butynal is proposed which features dissociation from the hot S₀ ground state by a concerted reaction.     

Non-radiative processes of benzaldehyde vapour: excitation energy dependence of the phosphorescence quantum yield in the presence of a foreign gas

The phosphorescence quantum yield of benzaldehyde vapour has been measured as a function of excitation energy and pressure (1–300 Torr) of nitrogen as a foreign gas. It is shown that the yield varies greatly as the excitation energy is varied from S₀→S₂ to S₀→S₃, indicating that benzaldehyde excited into S₃ decays by a non-radiative process which is different from that taken by the molecule excited into S₂.     

Fluorescence of 5-fluorouracil upon the transition from the second singlet excited state <Emphasis Type="Italic">S</Emphasis><Subscript>2</Subscript> to the ground state

Effect of the wavelength of excitation light (λ_ex) on the fluorescence excitation and emission spectra of 5-fluorouracil in acidic solution (pH 2.5) was studied upon excitation at the S ₂ ← S ₀-transition absorption band. It has been found that direct excitation at the second or the shorter wavelength absorption band results in 5-fluorouracil fluorescence that originates not only from the first excited state S ₁ but is also due the transition from the second excited state S ₂ to the ground state.     

The correlation of multiplets in different electronic transitions of 1, 12 benzperylene in solid matrices

Using a selective excitation technique, the correspondence of multiplet structure of spectra in the S₁←S₀, T₁→S₀ and S₂←S₀ electronic transitions of the 1, 12 benzperylene molecule in various matrices at 4.2 K is studied. The occurrence of an ambiguous correspondence of different electronic transition energies is pointed out. The reason for the lack of the sharpening of phosphorescence spectra under the monochromatic S₁←S₀ excitation is discussed.     

Low-temperature synthesis of fine BaMgAl10O17:Eu phosphor based on the solubility isotherms

A homogeneous and stoichiometric BaMgAl₁₀O₁₇:Eu²⁺ (BAM) phosphor powder has been prepared by the citrate route. Solubility isotherms have been calculated for metal-citric acid-water system at 25 °C to predict the optimum pH condition, which was found to be pH=7 for preparing pure and stable metal citrate complexes. Well crystallized and sub-micrometer-sized BAM particles could be obtained by thermal decomposition of the optimally prepared citrate precursor at a temperature as low as 1150 °C. Though the luminescent properties of the present samples under UV excitation well reflect the bulk properties, VUV excitation has exhibited the luminescent properties greatly influenced by the surface, which might be due to the fine particle. The maximum luminance of the samples heat treated at 1350 °C was 105% in comparison with that of the commercial BAM under VUV excitation.     

Time-resolved photoelectron studies of the relaxation of the S1(1E′') excited state of sym-triazine

We present photoelectron spectra of the lowest singlet state (¹E′') of sym-triazine obtained with 2 ns and 5 ps excitation sources. Comparisons of picosecond and nanosecond spectra are made at three wavelengths, corresponding to the 6₀¹, 6₀² and the 6₀¹12₀¹ vibrational levels. The spectra show that rapid (</ 5 ps) relaxation to the lowest triplet state occurs subsequent to singlet excitation. Coupling of S₁ levels to the T₁ manifold is very inhomogeneous with intersystem crossing rates ranging from 10⁷ s⁻¹ to > 10¹¹ s⁻¹. Furthermore, for excitation at the 6₀¹12₀¹ level we find evidence for relaxation to another excited state at rates ⩾ 10¹¹ s⁻¹.     

Electronic structure and optical properties of isolated and TiO2-grafted free base porphyrins for water oxidation: A challenging test case for DFT and TD-DFT

Seven free base porphyrins employed in dye-sensitized photoelectrosynthetic cells are investigated with the aim of benchmarking the ability of different density functional theory (DFT) and time-dependent DFT approaches in reproducing their structure, vertical, and E_0-0 excitation energies and the energy levels alignment (red-ox properties) at the interface with the TiO₂. We find that both vertical and E_0-0 excitation energies are accurately reproduced by range-separated functionals, among which the ω B97X-D delivers the lowest absolute deviations from experiments. When the dye/TiO₂ interface is modeled, the physical interfacial energetics is only obtained when the B3LYP functional is employed; on the other hand, M06-2X (54% of exchange) and the two long-range corrected approaches tested (CAM-B3LYP and ω B97X-D) excessively destabilize the semiconductor conduction band levels with respect to the dye's lowest unoccupied molecular orbitals (LUMOs), predicting no pathway for electron injection. © 2019 Wiley Periodicals, Inc.     

Efficient Coherent Population Transfer of D2 Molecules by Stark-induced Adiabatic Raman Passage

Preparation of a high flux of hydrogen molecules in a specific vibrationally excited state is the major prerequisite and challenge in scattering experiments that use vibrationally excited hydrogen molecules as the target. The widely used scheme of stimulated Raman pumping suffers from coherent population return which severely limits the excitation efficiency. Re-cently we successfully transferred D₂ molecules in the molecular beam from (v=0, J=0) to (v=1, J=0) level, with the scheme of Stark-induced adiabatic Raman passage. As high as 75% of the excitation efficiency was achieved. This excitation technique promise to be a unique tool for crossed beam and beam-surface scattering experiments which aim to reveal the role of vibrational excitation of hydrogen molecules in the chemical reaction.     

Close-coupling elastic and inelastic integral and differential cross sections for Li+ + H2 collisions

The quantum mechanical close-coupling formalism is applied to the study of elastic and rotationally inelastic Li⁺ + H₂ collisions making use of the Kutzelnigg-Staemmler-Hoheisel potential energy surface. Integral and differential cross sections for j = 0 → 0 and j = 0 → 2 are obtained in the collision energy range 0.2 to 0.9 eV and for j = 1 → 1 and j = 1 → 3 at 0.6 eV. A rainbow structure is observed in both the elastic and inelastic angular distributions and a quenching of the fast oscillations is found in the cross sections for j = 1 initially compared to the case j = 0 initially. At 0.6 eV. the calculated quantum mechanical angular distributions are compared to those from a classical trajectory calculation using the same surface and to the experimental ones. The dynamics of rotational excitation in the Li⁺ + H₂ system is contrasted to rotational excitation in systems for which the atom-diatom interaction is predominantly repulsive.     

Flash photolysis in Eu2+ doped NaCl

The luminescence of NaCl:Eu under flash-lamp and N₂-laser excitation has been studied. It has been found an anomalous non-exponential luminescence decay which follows a dependence I=I₀t^m with m=1 at low (90K) and room temperatures. The observed kinetics is consistent with a tunneling mechanism involving recombination of electrons and holes (V_k) at Eu sites.     

FRET‐Based Mitochondria‐Targetable Dual‐Excitation Ratiometric Fluorescent Probe for Monitoring Hydrogen Sulfide in Living Cells

Hydrogen sulfide (H₂S) is connected with various physiological and pathological functions. However, understanding the important functions of H₂S remains challenging, in part because of the lack of tools for detecting endogenous H₂S. Herein, compounds Ratio‐H₂S 1/2 are the first FRET‐based mitochondrial‐targetable dual‐excitation ratiometric fluorescent probes for H₂S on the basis of H₂S‐promoted thiolysis of dinitrophenyl ether. With the enhancement of H₂S concentration, the excitation peak at λ≈402 nm of the phenolate form of the hydroxycoumarin unit drastically increases, whereas the excitation band centered at λ≈570 nm from rhodamine stays constant and can serve as a reference signal. Thus, the ratios of fluorescence intensities at λ=402 and 570 nm (I₄₀₂/I₅₇₀) exhibit a drastic change from 0.048 in the absence of H₂S to 0.36 in the presence of 180 μM H₂S; this is a 7.5‐fold variation in the excitation ratios. The favorable properties of the probe include the donor and acceptor excitation bands, which exhibit large excitation separations (up to 168 nm separation) and comparable excitation intensities, high sensitivity and selectivity, and function well at physiological pH. In addition, it is demonstrated that the probe can localize in the mitochondria and determine H₂S in living cells. It is expected that this strategy will lead to the development of a wide range of mitochondria‐targetable dual‐excitation ratiometric probes for other analytes with outstanding spectral features, including large separations between the excitation wavelengths and comparable excitation intensities.     

Simulated ion trajectory and induced signal in ion cyclotron resonance ion traps. Effect of ion initial axial position on ion coherence,induced signal,and radial or z ejection in a cubic trap

The effects of ion initial axial position on coherence of ion motion, induced ion cyclotron resonance (ICR) signal. and radial and z ejection have been evaluated by numerical simulation for a cubic Fourier transform-ion cyclotron resonance ion trap. For a given initial ion cyclotron phase and radius, ions of different initial z position are shown to be excited to significantly different ion cyclotron radii (and ultimately radially ejected at significantly different excitation amplitude-duration products). Ion initial z displacement from the trap midplane affects observed ICR signal magnitude in two ways: (1) for the same postexcitation cyclotron radius, an ion with larger initial z displacement induces a smaller ICR signal and (2) an ion with larger initial z displacement is excited to a smaller cyclotron radius. We also evaluate the induced ICR signal as a function of excitation amplitude-duration product for spatially uniform or Gaussian ion initial z distributions. In general, if the excitation waveform contains components at frequency, 2 ω_z or (ω₊ + 2 ω_z, in which ω_z is the axial C“trapping”) oscillation frequency, then ejection occurs axially. However, the resulting excitation amplitude-duration product for such axial ejection is significantly higher (factor of, ～ 4) than that required for radial ejection (at ω₊) for ions of small initial radius. The present results offer the first explanation of how, even if the ion is initially at rest on the z axis (i.e., zero excitation electric field amplitude on the z axis), z ejection (axial ejection) may nevertheless occur if the excitation waveform contains frequency components at ω₊ + 2ω_z and/or 2_{w z} Namely, our simulations reveal that off-resonant excitation pushes ions away from the z axis, after which the ions are exposed to z excitation and eventual z ejection.     

Synthesis and luminescent properties of Tb-activated yttrium indium germanate phosphor

An yttrium indium germanate YInGe₂O₇ and YInGe₂O₇:Tb³⁺ was synthesized using a vibrating milled solid-state reaction with metal oxides. The structure was characterized by its X-ray powder diffraction pattern. All of the peaks can be attributed to the monoclinic YInGe₂O₇ phase, as increasing the Tb³⁺ ion concentrations and the full-width of the half-maximum (fwhm) of these peaks did not cause any obvious differences in the increase in Tb³⁺ concentration. The CIE color coordinates were all in the green region. The phosphor exhibited a bright green emission at 542 nm under excitation at 378 and 258 nm, which belongs to the ⁵D₄→⁷F₅ transition of Tb³⁺ ions. There were two kinds of emission mechanism in YInGe₂O₇:Tb³⁺: (1) under excitation at 378 nm, time-resolved ⁵D₄→⁷F₅ transition shows a single exponential decay even when all sites are occupied by Tb³⁺ ions; (2) under excitation at 258 nm, the excited energy was absorbed by the host crystal then transferred effectively to the Tb³⁺ ion which caused the decay curves for the ⁵D₄→⁷F₅ transition to show non-exponential behavior. There is a maximum value for photoluminescence intensity when the Tb³⁺ concentration is 100 mol% with CIE color coordinates of x=0.252; y=0.595. The concentration quenching effect was not observed, because the YInGe₂O₇:Tb³⁺ structure gradually changed to a thortveitite-like structure with increasing Tb³⁺ concentration.     

Room-Temperature Synthesized Cd-Doped Cs3Cu2I5: Stable and Excitation-Wavelength Dependent Dual-Color Emission for Advanced Anti-Counterfeiting

With the development of intellectual properties, concern about advanced anti-counterfeiting is accumulating, which conventional single-modal luminescence can no longer satisfy. As one of rapidly developing 0D materials, copper-based perovskite shows great potential to realize multiple luminescent centers for complex emissions. In this work, Cd was doped into Cs₃Cu₂I₅ and showed resultant emission at 560 nm which surprisingly showed a red-shifted excitation peak from that of intrinsic self-trapped emission, resulting in excitation-wavelength dependent emission. When the excitation wavelength increased from 290 nm to 330 nm, the emission of Cd-doped Cs₃Cu₂I₅ changed from deep blue to cold white and finally yellow. Afterwards, Cd-doped Cs₃Cu₂I₅ was mixed with polystyrene to prepare anti-counterfeiting ink for silk-screen printing. Meanwhile, Cd-doped Cs₃Cu₂I₅ maintains outstanding stability after doping, no matter under ambient, continuous UV radiation or high-temperature environment. The intensity can be almost totally recovered after heating-and-cooling cycles. This study lays groundwork for future research into multiple luminescent center manipulation in 0D materials.     

Effect of Reagent Rotational Excitation on Dynamics of F+H2→HF+H

The dynamics of the F+H₂(v=0,j=0, 1) reactions have been studied at the collision energy of 1.27 kcal/mol using a high-resolution crossed molecular beam apparatus. HF product rotational state resolved differential cross sections have been obtained at the v′=1, 2, 3 levels. The product HF(v′=2) angular distributions are predominantly backward scattered for both H₂ (j=0, 1) reagents. However, the distributions of product HF(v′=2) rotational states for theF+H₂(v=0,j=0) reaction are signi cantly di erent from those for the F+H₂(v=0,j=1) reaction. Experimental results show that the rotational excitation of H₂ produces rotationally ‘hotter’ HF(v′=2) product. In addition, the HF(v′=3) product is more likely scattered into the forward direction when the H₂ reagent is populated at j=0 state, which could be attributed to a slow-down mechanism.     

Vacuum ultraviolet absorption and fluorescence excitation spectra of Br2

Absorption and fluorescence excitation spectra of Br₂ in the region 125–170 nm have been recorded using tunable synchrotron radiation. Computer simulations of the absorption and dispersed fluorescence spectra have allowed identification of the upper electronic state responsible for the main fluorescence excitation system (150–167 nm), as the D(0⁺_u) ion-pair state. A potential function for this state is presented which accounts for vibrational levels up to ν′ ≈ 170 and a pronounced inflection on the inner wall of this potential, due to an avoided crossing, is identified at T_e + 15000 cm⁻¹. The mean radiative lifetime of the D(0⁺_u) state has been determined as ≈ 9 ns. An analysis of the 320–360 nm structured continuum fluorescence, from the D(0⁺_u) state to a lower repulsive state, is also given.     

Microwave synthesis and characterization of europium complexes with cinnamic acid and phenanthroline

We report here the synthesis and characterization of a host of Eu(Phen)L₃ with cinnamic acid (C₆H₅CH = CHCOOH, HL) and phenanthroline (Phen), and employing microwave radiation, where the microwave radiation is used just for the uniform heating of the reaction mixture. Its IR absorption spectra, scanning electron microscopy (SEM), and fluorescence spectra were studied. The results show that the particles of Eu(Phen)L₃ phosphors are basically spherical in shape, with good dispersing. The mean particle size is 1–2 μm. The excitation spectrum is a broad band and the main peak is at 320.0 nm. Moreover, excitation peak at 396.0 nm was found in the excitation spectrum. The emission spectrum shows that Eu(Phen)L₃ has narrow emission peaks. The emission peaks are ascribed to Eu³⁺ ions transition from ⁵ D _J (J = 0) to ⁷ F _J (J = 1, 2, 4). However, the strongest main emission peak locates at 614.0 nm, which corresponds to the electric dipole transition of Eu³⁺(⁵ D ₀ → ⁷ F ₂) The article is published in the original.     

Solution Chemistry of Europium(III) Aqua Ion at Micromolar Concentrations as Probed by Direct Excitation Luminescence Spectroscopy

Direct excitation europium(III) luminescence spectroscopy is used to study the speciation of aqueous europium(III) ions at micromolar concentrations and near neutral pH. The pH and concentration dependence of the europium(III) ⁷F₀→⁵D₀ excitation peak is consistent with the formation of both mononuclear and dinuclear europium(III) hydroxide complexes at pH 6.5. Luminescence intensity and lifetime quenching studies in the presence of Nd^III at pH 5.0 and 6.5 support the formation of a dinuclear complex at pH 6.5. Steady state excitation and time‐resolved luminescence spectroscopy are consistent with the formation of innersphere nitrate and fluoride complexes, but outersphere perchlorate and chloride complexes at pH 6.5 and 5.0.