VUV electronic state spectroscopy of 1,1-difluoroethene and difluorochloromethane by high resolution synchrotron radiation

High resolution VUV photoabsorption spectra of 1,1-difluoroethene (C(2)H(2)F(2)) and difluorochloromethane (CF(2)HCl) are reported in the wavelength range 115-200 nm (10.8-6.2 eV). New photoabsorption features are observed in C(2)H(2)F(2) and some Rydberg and vibrational assignments are proposed for the first time. Evidence for a weak vibrational pattern in CF(2)HCl is discussed here for the first time. Absolute cross section values have been obtained allowing photolysis lifetimes to be derived in the Earth's troposphere and stratosphere.     

Mass-analyzed threshold ionization study of vinyl bromide cation in the first excited electronic state using vacuum-ultraviolet radiation generated by four-wave mixing in Hg

The vibrational spectrum of the vinyl bromide cation in the first excited electronic state A 2A' was obtained by one-photon mass-analyzed threshold ionization (MATI) spectroscopy. The use of an improved vacuum-ultraviolet radiation source based on four-wave sum frequency mixing in Hg resulted in excellent sensitivity for MATI signals. From the MATI spectrum, the ionization energy to the A 2A' state of the cation was determined to be 10.9150+/-0.0006 eV. Nearly complete vibrational assignments for the MATI peaks were possible by utilizing the vibrational frequencies and Franck-Condon factors calculated at the density-functional theory (DFT) and time-dependent DFT/B3LYP levels with the 6-311+G(df,p) basis set.     

Identification of Intermediates in Pyridine Pyrolysis with Molecular-beam Mass Spectrometry and Tunable Synchrotron VUV Photoionization

The pyrolysis of pyridine （5.26% pyridine in argon） was performed with tunable synchrotron vacuum ultraviolet photoionization and molecular-beam mass spectrometry technique at the temperature range of 1255-1765 K at 267 Pa. About 20 products and intermediates, containing major species H2, HCN, C2H2, C5H3N, C4H2, and C3H3N, were identified by near-threshold measurements of photoionization mass spectra and their mole fractions vs. temperatures were estimated. The major reaction pathways are analyzed based on the experimental observations.     

VUV absorption and its relation to the effects of ionizing corpuscular radiation

Elements of the physics of photoabsorption as well as of energy transfer from fast charged particles are discussed. Among the key notions there are oscillator-strength spectra, quantum yields, and action spectra. Throughout the discussion, emphasis is put on the important role of soft X-rays and VUV light as obtained from a synchrotron radiation source in the understanding of actions of ionizing radiations in general.     

Resolving the emission times of solute and solvent four-wave mixing signals by spectral interferometry

Electric field-resolved transient grating measurements are used to distinguish the four-wave mixing signal emission from a resonant solute and a non-resonant solvent. The two components of the solution (i.e., solute and solvent) emit signal fields at different times with respect to the arrival of the probe pulse to the sample. This gives rise to a recurrence in the temporal profile of the total signal field. We show that the origin of this interference is the difference in relaxation time scales of the holographic gratings associated with the solute and solvent. The grating of the resonant solute relaxes on the time scale of a few picoseconds due to depopulation of its excited electronic state, whereas the electronic polarizability response of the solvent relaxes on the femtosecond time scale. This separability of responses is a general phenomenon that is particularly useful for studying weakly absorbing solute dynamics in polarizable solvents.     

Sensitivity and correlation analysis of the physical parameters in absorption,four-wave mixing,and Schlieren experiments

Experimental data that are used to determine rate coefficients depend not only upon reaction rates but also the physical properties of the measured species. Sensitivity coefficients are presented for the physical parameters of three general experimental techniques: a signal linearly dependent on the concentration of a species, a signal quadratically dependent on concentration, and a schlieren signal, which depends upon a bulk property of the system. With these, both the physical and chemical parameters of a model may be treated on a comparable basis. The similarities and differences between these techniques are illustrated in a simple example of radical formation via first-order precursor decomposition followed by second-order recombination. The results are then applied to two important examples: H₂ + O₂ and CH₃ + CH₃. In almost all cases, the experimental data contains more information about the physical parameters, such as the optical cross section, than the kinetic rate coefficients. Furthermore, if a physical parameter is not properly treated; strong correlations between it and rate coefficients will introduce significant systematic biases in the rate coefficient. © 1995 John Wiley & Sons, Inc.     

Direct determination of the ionization energies of FeO and CuO with VUV radiation

Photoionization efficiency curves were measured for gas-phase FeO and CuO using tunable vacuum-ultraviolet radiation at the Advanced Light Source. The molecules are prepared using laser ablation of a metal-oxide powder in a novel high-repetition-rate source and are thermally moderated in a supersonic expansion. These measurements provide the first directly measured ionization energy for CuO, IE(CuO)=9.41 +/- 0.01 eV. The direct measurement also gives a greatly improved ionization energy for FeO, IE(FeO) = 8.56 +/- 0.01 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to a refined bond strength for the FeO cation: D0(Fe(+)-O)=3.52 +/- 0.02 eV. A dramatic increase in the photoionization cross section at energies of 0.36 eV above the threshold ionization energy is assigned to autoionization and direct ionization involving one or more low-lying quartet states of FeO+. The interaction between the sextet ground state and low-lying quartet states of FeO+ is key to understanding the oxidation of hydrogen and methane by FeO+, and these experiments provide the first experimental observation of the low-lying quartet states of FeO+.     

Electronic spectra of radicals in a supersonic slit-jet discharge by degenerate and two-color four-wave mixing

Four-wave mixing techniques have been used for the measurement of electronic transitions of cold transient species generated in a supersonic slit-jet discharge expansion. The origin band of the d(3)Pi(g)-a(3)Pi(u) system of C(2) and A(2)Pi(3/2)-X[combining tilde](2)Pi(3/2) electronic transition of HC(4)S were recorded. A signal-to-noise ratio of 10(4) in the spectra was achieved, resulting in detection limits of 10(10) cm(-3) for these two molecules. Application of selective two-color resonant four-wave mixing is used for the spectral assignment utilizing the double-resonance nature of the method. The combination of these techniques with a slit source proves to be a sensitive approach for the detection of transient molecules in a molecular beam discharge.     

Insights into the structure of cyclohexane from femtosecond degenerate four-wave mixing spectroscopy and ab initio calculations

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes.     

To the theory of the mechanism of mixing in turbulent flows with coherent structures

A system of linear equations has been obtained which govern the yields of velocity and of the scalar passive impurity in a turbulent incompressible liquid flow. This system is considered as a simple model characterizing the large-scale coherent structures which have been found experimentally in many turbulent flows. The means to account for these structures when describing the mechanism of mixing are discussed.     

Efficient method for the calculation of time- and frequency-resolved four-wave mixing signals and its application to photon-echo spectroscopy

An efficient method has been developed for the calculation of third-order time- and frequency-resolved optical signals. To obtain the general four-wave mixing signal, seven auxiliary density matrices have to be propagated in time. For the special cases of two-pulse photon-echo and transient-grating signals, two or three density matrices, respectively, are required. The method is limited to weak laser fields (it is thus valid within the third-order perturbation theory) but allows for any pulse durations and automatically accounts for pulse-overlap effects. To illustrate the method, we present the explicit derivation of the three-pulse photon-echo signal. Any other third-order optical signal can be calculated in the same manner. As an example, two- and three-pulse photon-echo and transient-grating signals for a weakly damped displaced harmonic oscillator have been calculated.     

Plutonium-244 fission xenon and primordial xenon in the Allende meteorite

The carbonaceous chondrite Allende contains (22±1)·10⁻¹² cm³STP/g of²⁴⁴Pu fission xenon and two kinds of primordial xenon: Type I and Type II. The former represents the isotopic composition of a primordial xenon, which resided in the vicinity of a supernova shortly before it exploded, while the latter represents that of the xenon, which resided in the supernova. The isotopic composition of xenon found in the pink inclusion of the Allende meteorite, corrected for the presence of very large excesses of²⁴⁴Pu fission xenon,¹²⁹Xe from the decay of¹²⁹I, and of¹²⁸Xe from the neutron-capture reactions on¹²⁷I, resembles that of Type-I primordial xenon. The isotopic composition of xenon found in the diamond inclusions of the Allende meteorite, on the other hand, represents that of Type-II primordial xenon and it resembles that of a mixture of Type-I primordial xenon whose isotopic composition is severely altered by a combined effect of (a) mass-fractionation, (b) spallation, (c) stellar-temperature neutron-capture reactions, and (d) the presence of a large excess of²⁴⁴Pu fission xenon.     

Eu(III) complex-doped PMMA having fast radiation rate and high emission quantum efficiency

Three ternary luminescent complexes, Eu (deuterated 1,3-diphenyl-1,3-propanedione)₃(1,10-phenanthroline), Eu (deuterated 1,3-diphenyl-1,3-propanedione)₃(2,2′-bipyridine), and Eu (deuterated 1,3-diphenyl-1,3-propanedione)₃ (bathophenanthroline) were synthesized using bidental oxygen and nitrogen as ligands. Luminescent polymers were fabricated by incorporating deuterated Eu(III) complexes in a poly(methyl methacrylate) matrix. Luminescent poly(methyl methacrylate) containing Eu (deuterated 1,3-diphenyl-1,3-propanedione)₃ (bathophenanthroline) exhibited relatively higher quantum yield, faster radiation rate, sharper red emission and larger stimulated emission cross-section (quantum yield 36%, radiation rate 8.6 × 10² s^?1, full width at half maximum 3.4 nm, and stimulated emission cross-section σ _p = 1.4 × 10^?20 cm²) of the PMMA matrix. The value of σ _p was the same order as the values of Nd-glass laser for practical use. Additionally, the thermal behaviors of the Eu(III) ternary complexes were studied, and the results indicated that all of them can be long-term used in high temperature environment. Prepared luminescent polymer including Eu (deuterated 1,3-diphenyl-1,3-propanedione)₃ (bathophenanthroline) showed promising results for applications in novel organic Eu(III) devices, such as high-power laser materials and optical fibers.     

An implementation of the Deutsch–Jozsa algorithm on molecular vibronic coherences through four-wave mixing: a theoretical study

Time-frequency resolved coherent anti-Stokes Raman scattering (TFRCARS) was recently proposed as a means to implement quantum logic using the molecular ro-vibrational manifold as a quantum register [R. Zadoyan et al., Chem. Phys. 266 (2001) 323]. We give a concrete example of how this can be accomplished through an illustrative algorithm that solves the Deutsch–Jozsa (DJ) problem. We use realistic molecular parameters to recognize that, as the problem size expands, shaped pulses must be tailored to maintain fidelity of the algorithm.     

Selective and reversible control of a chemical reaction with narrow-band infrared radiation: HXeCC radical in solid xenon

The light-induced H + XeC2 <--> HXeCC reaction is studied in solid Xe, and the full optical control of this reaction is demonstrated. By narrow-band excitation in the IR spectral region, HXeCC radicals can be decomposed to a local metastable configuration and then selectively recovered by resonant excitation of the XeC2 vibrations. The novel recovery process is explained by short-range mobility of the reagents promoted by vibrational energy redistribution near the absorbing XeC2 molecule. This means that a chemical reaction can be selectively promoted in a desired place where the chosen absorber locates. The obtained results make a strong case of solid-state reactive vibrational excitation spectroscopy of weak radiationless transitions.     

Spectral and kinetic studies of the second continuum fluorescence of xenon excited by synchrotron radiation

Synchrotron radiation at LURE has been used to excite xenon in the pressure range of 50 to 200 torr. The subsequent second continuum fluorescence at 1720 Å has been spectrally and temporally analyzed. The observed two-component decay of this emission, as well as various spectral features, are shown to be in disagreement with some results previously reported in the literature.     

Direct determination of the ionization energies of PtC, PtO, and PtO2 with VUV radiation

Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements provide the first directly measured ionization energy for PtC, IE(PtC) = 9.45 +/- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +/- 0.1 eV and IE(PtO2) = 11.35 +/- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly improved 0 K bond dissociation energies for the neutrals: D0(Pt-C) = 5.95 +/- 0.07 eV, D0(Pt-O) = 4.30 +/- 0.12 eV, and D0(OPt-O) = 4.41 +/- 0.13 eV, as well as enthalpies of formation for the gas-phase molecules DeltaH(0)(f,0)(PtC(g)) = 701 +/- 7 kJ/mol, DeltaH(0)(f,0)(PtO(g)) = 396 +/- 12 kJ/mol, and DeltaH(0)(f,0)(PtO2(g)) = 218 +/- 11 kJ/mol. Much of the error in previous Knudsen cell measurements of platinum oxide bond dissociation energies is due to the use of thermodynamic second law extrapolations. Third law values calculated using statistical mechanical thermodynamic functions are in much better agreement with values obtained from ionization energies and ion energetics. These experiments demonstrate that laser ablation production with direct VUV ionization measurements is a versatile tool to measure ionization energies and bond dissociation energies for catalytically interesting species such as metal oxides and carbides.     

Vertical mixing and ecological effects of ultraviolet radiation in planktonic communities

We present a mathematical model for a phytoplankton-zooplankton system, based on a predator-prey scheme. The model considers the effects of sinking in the phytoplankton, vertical mixing and attenuation of photosynthetically active radiation (PAR) and ultraviolet radiation (UVR) in the water column. In a first approach, the model was studied under conditions of average PAR irradiance and shows fluctuations and stable equilibrium points. Secondly, we introduced the effects of photoperiod and photoinhibition by UVR and vertical mixing. Under these conditions, the phytoplankton biomass oscillates depending on the combined effects of UVR and mixing. Higher inhibition by UVR and longer mixing periods can induce strong fluctuations in the system but can also produce higher plankton peaks.     

Forward-scattering degenerate four-wave mixing as a potential laser-based absorption detection method in liquid separation systems: Coupling to conventional-size liquid chromatography

An explorative study on the compatibility of liquid separation systems, such as (micro) liquid chromatography (LC) and capillary electrophoresis (CE), and forward-scattering degenerate four-wave mixing (F-D4WM) as a detection method is presented. F-D4WM is a laser-based technique showing some analogy with holographic spectroscopy: a signal on a theoretical dark background is observed as a result of light absorption by an analyte. Parameters considered are solvent composition focussing on acetonitrile, methanol and water; mobile phases in LC and CE), detector cell construction, and influences of laser beam powers. A specially designed detector cell has been developed to meet the Brewster condition, both at the air-quartz and the quartz-liquid boundaries. For practical reasons, the tested cell has an optical pathlength of 1 mm; reduction to 100 μm is required to apply the cell in microseparations. The F-D4WM technique has been involved for detection in a conventional-size, reversed-phase LC separation of 1- and 2-aminoanthraquinones. The detection limit obtained (for the 1 mm cell) is 2 × 10⁻⁵ absorbance units. The experiments indicate that further reduction of background deserves explicit attention.