Photofragmentation of the K-shell excited perfluorocyclobutane: anisotropies in the fragments and breakdown pathways

Total ion yield spectrum of perfluorocyclobutane (c-C(4)F(8)) has been measured in the C and F K-shell excitation regions. The peak assignments are presented based on angle-resolved photofragment ion mass spectrometry. The peaks at 291.34 and 688.5 eV are found to come from the transitions from the C 1s and the F 1s to the lowest unoccupied b(2)σ(CF)* orbital, respectively. A photoelectron-photoion-photoion coincidence spectrum is acquired at 700.1 eV for clarifying the breakdown pathways of c-C(4)F(8)(2+). Two series of the pathways are identified; fission of F atom(s) followed by charge separation and elimination of CF(2) or CF(3) followed by charge separation.     

Electronic structure of excimer molecular lasers

The electronic structure, potential energy curves, and radiative transition probabilities of excimer systems have been examined using quantum mechanical methods. These molecules are characterized by repulsive or weakly bound ground state potential curves and by bound, strongly ionic, or Rydberg, excited states. They constitute a very interesting class of molecules which offer the possibility for high power, high efficiency UV laser operation. Calculations have been carried out using the density functional SCF -X_α method, modified extensively to correct for well known errors arising from approximations to the potential and exchange terms. A limited number of ab initio calculations were also carried out for comparison purposes. For the ArF system we find that the lowest excited ionic state has symmetry ²∑${}_{\text{½}}^{\text{+}}$ , and that the dominant laser transition observed at 1933 Å should be assigned to B ²∑${}_{\text{½}}^{\text{+}}$ → X ²∑${}_{\text{½}}^{\text{+}}$ . The C ²Π_3/2 → X ²∑${}_{\text{½}}^{\text{+}}$ transition is calculated to be two orders of magnitude smaller in emission intensity than the dominant transition, thus ruling out this assignment for the observed laser line in ArF. Preliminary calculations carried out for Ar₂F indicate that the bound upper ionic state has ²B₂ symmetry and that the most probable ground state also has ²B₂ symmetry. This polyatomic system is predicted to exhibit a broadband emission spectrum with a relatively long radiative lifetime.     

Photofragmentation of nitro-based explosives with chemiluminescence detection

A simple, fast, reliable, sensitive and potentially portable explosive detection device was developed employing laser photofragmentation (PF) followed by heterogeneous chemiluminescence (CL) detection. The PF process involves the release of NO_{x(x = 1,2)} moieties from explosive compounds such as TNT, RDX, and PETN through a stepwise excitation–dissociation process using a 193 nm ArF laser. The NO_{x(x = 1,2)} produced upon PF is subsequently detected by its CL reaction with basic luminol solution. The intensity of the CL signal was detected by a thermoelectrically cooled photomultiplier tube with high quantum efficiency and negligible dark current counts. The system was able to detect trace amounts of explosives in various forms in real time under ambient conditions. Detection limits of 3 ppbv for PETN, 2 ppbv for RDX, and 34 ppbv for TNT were obtained. It was also demonstrated that the presence of PETN residue within the range of 61 to 186 ng/cm² can be detected at a given signal-to-background ratio of 10 using a few microjoules of laser energy. The technique also demonstrated its potential for the direct analysis of trace explosive in soil. An LOD range of 0.5–4.3 ppm for PETN was established, which is comparable to currently available techniques. Figure Photofragmentation–chemiluminescence detector     

Intramolecular excimer formation in macromolecules. I. Energy migration and excimer formation in copolymers exhibiting nearest-neighbor excimer interactions

Energy migration and intramolecular excimer formation have been studied in a series of copolymers comprising 1-vinylnaphthalene, 2-vinylnaphthalene, and styrene with methyl methacrylate. The technique of fluorescence depolarization was used to characterize energy migration in glassy solutions of the copolymers. The extent of energy migration in these copolymers is determined by the mean sequence length of aromatic species l?_a. Assuming that excimer formation occurs as a result of nearest-neighbor interactions, the concentration of excimer sites in the macromolecule will be proportional to the fraction of links between aromatic species f_aa. It is proposed that these sites are populated via energy migration from the site of absorption. Proportionality between the ratio of excimer to monomer emission intensities and the function l?_a·f_aa was predicted. Good agreement with this relationship was obtained in each of the copolymer systems studied. Reactivity ratios of methyl methacrylate (r_m) in copolymerization at 70°C with the aromatic monomers (r_a) were determined as: 1-vinylnaphthalene—r_m = 0.43, r_a = 1.71: 2-vinylnaphthalene—r_m = 0.37, r_a = 4.46; styrene-r_m = 0.45, r_a = 0.58.     

Photolysis and desorption of adsorbed halomethane molecules under long-wavelength radiation of excimer lasers

The photolysis and desorption of CH₂I₂, CH₃I, CCl₄, CHCl₃, CH₂Cl₂, CF₂Cl₂, and CHF₂Cl molecules adsorbed on fused silica under the action of XeF and XeCl laser radiation absorbed by these molecules have been studied. The desorption of molecules that occurs due to expansion to the long-wavelength region of the absorption spectrum of molecules in the adsorbed state, compared to the gas phase, predominates. The laser desorption is characterized by a strong nonlinear dependence on the density of radiation energy. Depending on the relationship between the laser radiation wavelength and the spectrum of electronic states of molecules, photolysis is observed upon absorption of either one or two photons. At an increased fluence of laser radiation energy, the one-photon detachment of the primary CH₂I fragment from the CH₂I₂ molecule changes into the three-photon process. A similar behavior is revealed for the desorption of CH₃I molecules from clusters formed on the surface in multilayer adsorption coverages.     

Thermal and Photofragmentation of N-Benzoylhydrazone Derivatives

Two selected benzoylhydrazones I and II were subjected to thermolysis by reflux at 200 °C. Benzil, benzoic acid, biphenyl, benzanilide together with the corresponding ketones, nitriles and imines were isolated. Similar treatment of the third hydrazone III at 250 °C afforded, in addition to the previous products, bibenzyl, stilbene, and 2-phenylindole. Photolysis of the same hydrazones I-III in acetonitrile gave the previously reported products but in different ratios along with azine derivatives and substituted methanes. A free radical mechanism involving homolysis of the N-N and C-N bonds is suggested, substantiated by trapping of phenyl radical with isoquinoline, to account for the formation of the identified products.     

On the electronic structure of CNCl and NOCl

The ionization potentials and relative X-ray intensities were calculated for CNCl and NOCl by means of an ab initio LCAO SCF program. The data obtained are compared with the Cl Kβ spectra which were recorded using a high-resolution curved crystal spectrograph. The agreement between theory and experiment is satisfactory and allows for a reliable assignment of the prominent spectral features to the corresponding molecular X-ray transitions. A strong conjugation of the Cl lone pair electrons with the π bonds of the CN group has been found for CNCl. In the case of NOCl a corresponding conjugation of the Cl lone pair electrons with the double bonds of the NO group is absent.     

Energy distributions of gallium nanoclusters

Starting with the heat-capacity data of Breaux et al., [J. Am. Chem. Soc. 126, 8629 (2004)] we use the maximum-entropy method to calculate energy distribution functions for gallium-ion nanoclusters over a wide temperature range (100-1050 K). Specifically, we calculate energy distributions for clusters containing n = 39 and n = 45 gallium atoms. For the case of n = 39 clusters the energy distribution gets systematically broader as a function of temperature with no indication of any marked structural change in the cluster. On the other hand, the energy distribution for the n = 45 cluster first gets broader as a function of temperature but then gets narrower again as the temperature is further increased, indicating that there is some kind of structural transition taking place in this cluster species.     

Photofragmentation of closo-carboranes part 1: Energetics of decomposition

The ionic fragmentation following B 1s and C 1s excitation of three isomeric carborane cage compounds [closo-dicarbadodecaboranes: orthocarborane (1,2-C2B10H12), metacarborane (1,7-C2B10H12), and paracarborane (1,12-C2B10H12)] is compared with the energetics of decomposition. The fragmentation yields for all three molecules are quite similar. Thermodynamic cycles are constructed for neutral and ionic species in an attempt to systemically characterize single-ion closo-carborane creation and fragmentation processes. Lower energy decomposition processes are favored. Among the ionic species, the photon-induced decomposition is dominated by BH+ and BH2(+) fragment loss. Changes in ion yield associated with core to bound excitations are observed.     

The relation of cluster ion distributions to neutral cluster distributions in cluster beam experiments

One of the major problems in cluster beam experiments with uncharged clusters is to relate the detected distribution of cluster ions to the original distribution of the neutrals. Fragmentation of the clusters, differences in ionization efficiencies, and desorption of ligands for chemically reacted clusters distort the initial distribution. In this contribution the abundances of the neutral and the ionized particles will be related by rate equations in terms of phenomenological rate constants. Two approaches are chosen. In the more simple one the ionization and decay processes are fast and take place during the excitation pulse. In the second approach delayed processes are also allowed. In both cases recursion formulas are derived as analytical solutions of the coupled rate equations for the time evolution of the neutral and ionized cluster intensities. The general solutions contain a considerable number of parameters which have to be reduced by experimental conditions and observations. Applications are discussed.     

Sub-Doppler optical one-photon spectroscopy of binary mixtures of neutral,mutually interacting gases with lasers: dispersion spectra

We consider in this paper the optical, sub-Doppler high resolution dispersion spectra for one-photon transitions of a mixture of two different interacting gases. The gases are supposed to be neutral and each molecule of the mixture interacts with molecules of the same kind and with molecules of different kinds, via hard collisions. Those interactions are restricted to binary collisions treated in the so-called impact approximation. We calculate the dispersion optical sub-Doppler spectra of a weak laser beam in the presence of a strong, saturating, counterpropagating laser one. The optical fields of both lasers are supposed to be travelling electromagnetic plane monochromatic waves. The angular frequencies ω₁ and ω₂ of those waves are taken, in general as different. An appropriate parametrizing procedure of all the physical quantities involved for treating this problem is taken.     

Recombination of polycyclic aromatic hydrocarbon photoions with electrons in a flowing afterglow plasma

A new technique, flowing afterglow with photoions (FIAPI), has been developed to measure the rate coefficient for the recombination of complex ions, and, in particular, polycyclic aromatic hydrocarbon (PAH) cations with electrons. The method is based on the flowing afterglow Langmuir probe - mass spectrometer apparatus at the University of Rennes I. A helium plasma is generated by a microwave discharge in a He buffer gas and downstream, a small amount of argon gas is injected to destroy any helium metastables. A very small amount of neutral PAH molecules is added to the afterglow plasma by evaporation from a plate coated with the PAH to be studied. PAH ions are then produced by photoionization of the parent molecule using a pulsed UV laser (157 nm). The laser beam is oriented along the flow tube and so a constant spatial concentration of photoions is obtained. The electron concentration along the flow tube is measured by means of a movable Langmuir probe. Ion concentration decay in time is measured at a fixed position using a quadrupole mass spectrometer which is triggered by the laser pulse. The recombination of anthracene and pyrene cations has been studied using this technique and we have found a recombination rate of (2.4 +/- 0.8) x 10(-6) cm(3) s(-1) for anthracene and (4.1 +/- 1.2) x 10(-6) cm(3) s(-1) for pyrene.     

Building molecular charge distributions from fragments: Application to HIV-1 protease inhibitors

Interaction energies are a function of the molecular charge distribution. In previous work, we found that the set of atomic partial charges giving the best agreement with experimental vacuum dipole moments were from density functional theory calculations using an extended basis set. Extension of such computations to larger molecules requires an atomic partial charge calculation beyond present computational resources. A solution to this problem is the calculation of atomic partial charges for segments of the molecule and reassociation of such fragments to yield partial charges for the entire molecule. Various partitions and reassociation methods for five molecules relevant to HIV-1 protease inhibitors are examined. A useful method of reassociation is introduced in which atomic partial charges for a large molecule are computed by fitting to the combined electrostatic potential calculated from the fragment partial charges. As expected, the best sites for partitions are shown to be carbon—carbon rather than carbon—nitrogen bonds. © 1997 by John Wiley & Sons, Inc.     

Characterization of neutral fragments issued from the photodissociation of protonated tryptophane

New information on the photo-fragmentation of biomolecules is obtained from the detection of neutral and ionic fragments using a time and position resolved coincidence technique that reveals whether an ionic photofragment is associated with one or more neutral fragments. In the case of a sequential dissociation, both fragmentation channels are identified as well as their time ordering.     

Determination of energy and mass distributions of ions and neutral particles in magnetron-ionplating

Summary Energy distributions are presented of the ions produced in a magnetron plasma source which hit the negatively biased substrate surface thus getting deeper insight into the coating process. By observing the mass analysed fluxes and the energy distributions of the impinging particles it is found that practically only atomic ions and atomic neutrals arrive at the substrate and contribute to the growth of the film.     

Energy transfer and excimer formation in a flowing afterglow of Mg metastables

Mg atoms were vaporized into a fast flowing Ar carrier stream and then excited by an ac discharge. Downstream of the discharge in the afterglow region metastable Mg (³P) atoms were reacted with vaporized metals. The resultant chemiluminescence consisted of metal atom resonance lines and continuous emission bands of the molecule KMg.