State selective step-wise photoionization of NO with mass spectroscopic ion detection

State and isotope selective two-step photoionization of NO with mass spectroscopic ion detection has been demonstrated and investigated. Using saturation condition the photoionization cross section for a single rotational level of the intermediate state, No(A ²Σ⁺, ν′=0), has been measured: σ_i=(7.0±0.9) X 10⁻¹⁹ cm². The charge transfer¹⁵NO⁺+¹⁴NO→¹⁵NO+¹⁴NO⁺ has been observed and investigated, yielding a cross section of the order of 13×10⁻¹⁶ cm², consistent with recent measurements at about 1 eV.     

Laser multiphoton mass spectroscopy of organometallic compounds: State selective and mass resolved detection of neutral fragment tellurium atoms from C2H5TeC2H5

Typical features in laser multiphoton ionization of organometallic compounds are well evident in the case of the diethyltelluride C₂H₅TeC₂H₅ molecule. The use of a tunable dye laser coupled with time-of-flight (TOF) mass spectroscopy has allowed to establish that a large amount of tellurium is eliminated from the parent molecule as a neutral atom either in its ground or low excited states. Sharp two- and three-photon atomic Te resonances, which give origin to extraproduction of Te⁺ ions, have been identified in the optical spectra measured by varying the laser wavelength.     

Laser photoionization detection of the rare isotope3He

Based on combination of the two-step collinear isotope-selective photoionization and time-of-flight separation of atoms in a fast modulated beam, a new technique has been developed for detecting the³He rare isotope with an isotopic selectivity of up to 10¹⁰. The technique helped to detect optically, for the first time,³He at a relative abundance of 4·10^–8.     

Resonant two-step photoionization of molecules: Effects of pulse sequence,pulse duration and delay time of two lasers on ionization probability and selectivity

Using rate equations the effect of different pulse sequences, pulse durations, and delay times of two lasers on ionization probability and selectivity in resonant two-step photoionization of molecules is investigated. The results demonstrate to what extent a given selectivity of the absorption or relaxation of the intermediate electronic, state is influenced by a special combination of these parameters.     

Detection of neutral products formed during excimer laser ablation of polyimide by UV and VUV laser photoionization/mass spectrometry

Some of the neutral species which are produced in the laser ablation of polyimide have been characterized using multiphoton ionization/time of flight mass spectrometry. Three different wavelengths (193 nm, 157 nm, and 118 nm) have been used in an attempt to effect soft ionization of the products formed during or after the initial laser ablation of the polymer. Neutral photo-ablation products detected using this scheme range from atomic to high molecular weight species which, depending on the probe wavelength, include pure carbon clusters as well as a broad distribution of heteroatom containing clusters. However, there is virtually no overlap in the mass spectra recorded at each probe wavelength. When probing with 193 nm, marked changes are observed in the mass spectra as a function of the probe flux used. At moderate fluxes, pure carbon clusters (fullerenes) are observed. The identification of a large distribution of species other than pure carbon clusters is in dramatic contrast to the recent observation [W.R. Creasy, J.T. Brenna: Chem. Phys. 126, 453 (1988)] of the positively charged ionic species produced, which are solely carbon clusters. These results suggest that the neutral and ionic products observed after ablation of the polymer are due to both condensation of the atomic and molecular fragments which form during the ablation laser pulse and nascent polymer fragments. Various implications of this result for the unambiguous determination of the true ablation product distribution are discussed.     

Laser ion kinetics: set-up and application of a single-shot femtosecond pump–probe technique

In this contribution the first measurements of a single-shot femtosecond laser pump–probe technique are reported. The technique is based on counter-propagating femtosecond laser pulses in a supersonic beam of a low density of sample molecules and simultaneous probe detection by ion or fragment-ion formation through a reflectron time-of-flight mass spectrometer. It will be shown that the range of the pump–probe delays covers the time span between 100 fs and 10 ps depending on the pulse width of the laser used and the stability of the volt ages of the mass spectrometer. The application of this technique to organometallic compounds as well as to medium-sized organic molecules reveals some insight into the electron-transfer process during ionization through a 1+1 multi-photon absorption procedure. Furthermore it is demonstrated that this technique is also applicable to the investigation of ultra-fast isomerization and fragmentation processes. As an example the results of the processes within iron pentacarbonyl and substituted benzalacetones are reported. Received: 22 October 1999 / Published online: 24 July 2000     

Laser method of highly selective detection of rare radioactive isotopes through multistep photoionization of accelerated atoms

A laser detection method is proposed for ultralow abundance (<10^–10) of rare radioactive isotopes based on a multistep photoionization of accelerated atoms with a selectivity up to 10⁷ on each step of a collinear laser excitation.     

REMPI as a tool for studies of OH radicals in catalytic reactions

2 +? O₂→H₂O on polycrystalline Pt foils has been studied by detection of desorbing OH radicals using the Resonance Enhanced Multiphoton Ionization, REMPI, technique. The measurements were performed at catalyst temperatures of 1000–1400 K and a total pressure below 10^-4 mbar. The studies of OH desorption by REMPI were achieved using a two-photon excitation D²Σ^-–X²Π (1–0), followed by one-photon ionization. The ions were detected in a time-of-flight mass spectrometer, TOF-MS, in order to avoid interference from non-resonantly ionized molecules. By applying TOF-MS, a simultaneous non-resonant ionization and detection of H₂, O₂ and H₂O was achieved. Recorded REMPI spectra were compared with spectra simulated using known molecular constants. The kinetics of the reaction derived from the measurements were compared with what was obtained in earlier LIF detection of OH, performed at higher total reactant pressure using the A–X transition. REMPI TOF-MS is shown to be a complement to LIF for reaction studies below 5×10^-4 mbar total pressure, where LIF is too insensitive for quantification. The reaction kinetics was found to be in agreement with a theoretic model and previous LIF studies. Received: 8 March 1996/Revised version: 4 October 1996     

Time multiplexing: a new single shot femtosecond pump-probe technique

Received: 26 August 1996/Revised version: 13 November 1996     

Analysis of solids by secondary ion and sputtered neutral mass spectrometry

A mass spectrometer is described, which allows the analysis of sputtered neutral and charged particles as well as of residual gas composition. This combined SIMS, SNMS, and RGA instrument consists of a scanning primary ion beam column, an electron impact ionizer, an electrostatic energy filter and an rf quadrupole mass analyzer.Various examples of surface and bulk analysis are presented which demonstrate the beneficial complementary features of these techniques. These are, in particular: a substantial reduction of the matrix effect and fewer complications with samples of low electrical conductivity in SNMS, and the possibility of measuring the depth distribution of gases included in small cavities in the solid in the SNMS/RGA mode. SIMS, on the other hand, allows in many cases higher detection sensitivities.EURATOM Association     

Coupling of desorption and photoionization processes in two-step laser mass spectrometry of polycyclic aromatic hydrocarbons

The response of polycyclic aromatic hydrocarbons (PAHs) to different desorption and ionization fluences has been investigated in a laser desorption/multiphoton ionization/time-of-flight mass spectrometry scheme. The results evidence an intricate relationship between the desorption and ionization steps, tentatively attributed to the amount of internal energy acquired by the desorbed molecules. Different behaviors have been found for the various PAHs considered, leading to a parametric “signature” for each species. Moreover, some insights on the fragmentation mechanism of the desorbed PAHs have been obtained, with possible interpretation in the frame of a “ladder-switching” model.     

Measurements of235U/238U isotopic ratio in the photoproduct UF5 by multiphoton ionization and time-of-flight mass spectrometry

A MultiPhoton-Ionization Time-Of-Flight Mass Spectrometry (MPI/TOFMS) apparatus was developed for real-time measurement of the uranium isotopic ratio in nascent UF₅ formed by the 266 nm photolysis of effusive UF₆ ( < 300 K, 1.3 × 10^–4 Pa). The UF₅ was selectively and efficiently multiphoton ionized by 532 nm radiation at appreciably low fluences ( < 10 J/cm²). The main ions observed, U⁺ and U²⁺, were subsequently analyzed with a TOFMS with mass resolution of 1190 to separate²³⁵U ⁿ⁺ and²³⁸U ⁿ⁺ completely. The isotopic ratio measurements showed good precision resulting from the excellent agreement which was observed between the isotopic ratios in UF₅ products and those in a parent UF₆ sample. These results suggested that the MPI/TOFMS method can be applied to the real-time analysis of separation factors in the molecular laser isotope separation of uranium by ionization of UF₅ following the infrared photodissociation of UF₆.     

Influence of the photoionization process on the fragmentation of laser desorbed polycyclic aromatic hydrocarbons

Characterization of polycyclic aromatic hydrocarbons (PAHs) samples has been performed by laser desorption combined with multi-photon ionization technique using two different geometries of the ionization laser beam. This comparative study evidences the strong influence of ionization laser fluence on PAH fragmentation. Through a ∼10³ enlargement of the ionization probe volume and 10⁴ reduction of laser fluence over previous studies, fragment free mass spectra are obtained with higher sensitivity and selectivity. The ability to measure fragment free PAH mass spectra is a very important step in the end goal of measuring complex unknown mixtures of PAH desorbed from solid surface such as soot samples.     

Detection of NO traces Using resonantly enhanced multiphoton ionization: A method for monitoring atmospheric pollutants

Resonantly enhanced multiphoton ionization (REMPI) is proposed as an ultrasensitive detection method forreal-time monitoring of atmospheric pollutants in situ. The technique is demonstrated in the laboratory for NO diluted in pure nitrogen at 560 mbar. The MPI current resulting from (2+1) photon ionization of NO via the resonantC ² H (v=0) state has been measured for several NO concentrations. Detection levels as low as 50 ppt have been obtained.Laboratoire associé à l'Université de Paris-Sud     

Thin film characterization by laser interferometry combined with SIMS

Thin film properties of technologically important materials (Si, GaAs, SiO₂, WSi_x) have been measured by using a novel technique that combines secondary ion mass spectrometry (SIMS) and laser interferometry.The simultaneous measurement of optical phase and reflectance as well as SIMS species during ion sputtering yielded optical constants, sputtering rates and composition of thin films with high depth resolution. A model based on the principle of multiple reflection within a multilayer structure, which considered also transformation of the film composition in depth and time during sputtering, was fitted to the reflectance and phase data. This model was applied to reveal the transformation of silicon by sputtering with O ₂ ⁺ ions. Special attention was paid to the preequilibrium phase of the sputter process (amorphization, oxidation, and volume expansion). To demonstrate the analytical potential of our method the multilayer system WSi_x/poly-Si/SiO₂/Si was investigated. The physical parameters and the stoichiometry of tungsten suicide were determined for annealed as well as deposited films. A highly sensitive technique that makes use of a Fabry-Perot etalon integrated with a Michelson type interferometer is proposed. This two-stage interferometer has the potential to profile a sample surface with subangstroem resolution.     

Combustion chemistry probed by synchrotron VUV photoionization mass spectrometry

Combustion is directly related to energy conversion and the environment. Gas-phase chemical reactions such as thermal decomposition, oxidation and recombination play a critical role in combustion processes. Here we review six applications of synchrotron vacuum-ultraviolet (VUV) photoionization mass spectrometry (PIMS) in fundamental studies of combustion chemistry. These applications range from the use of flow reactors to probe elementary reaction kinetics, studies of pyrolysis in plug-flow reactors and oxidation in jet-stirred reactors, studies of spatial evolution of species concentrations in premixed and non-premixed flames, product distributions in pyrolysis of biomass, and analysis of polycyclic aromatic hydrocarbon (PAH) formation. These experiments provide valuable data for the development and validation of detailed chemical kinetic models. Furthermore, some additional potential applications are proposed.     

Self-action effects in ionization and fragmentation of toluene by femtosecond laser pulses

Occurrence and influence of several self-action effects, induced in the entrance window of a time-of-flight interaction chamber, on the ion and fragment yields of the toluene molecule in the focus of a Ti:sapphire laser pulse are analyzed. Experimental data are obtained using different focusing geometries and are compared with results from numerical simulations using a nonlinear pulse propagation model as well as those from the strong-field S-matrix theory. It is shown that (a) self-focusing leads to a displacement of the focus while amplified small perturbations of the input beam result in hot spots in the spatial distribution and in an energy-dependent focus area, (b) small self-phase modulation changes the form of the spectrum and broadens it slightly. A strong increase of the toluene fragmentation appears to correlate to linear and nonlinear changes in the focal spot area, while the scenario of excitation of Raman modes proposed in an earlier publication is ruled out as the dominant effect.This revised version was published online in March 2005. In the previous version, the published online date was missing     

Detection of explosive-related compounds by laser photoionization time-of-flight mass spectrometry

We report studies using laser photoionization and time-of-flight mass spectrometry to detect several explosive-related compounds (ERCs). The ultimate goal of this work is the detection of buried land mines through their chemical signatures. Resonantly enhanced multiphoton ionization using jet expansion cooling, with a nanosecond pulse laser, results in complete photofragmentation of the parent ERC and appearance only of the NO⁺ ion, which forms all of the detected signal. This will also occur for compounds naturally occurring in the environment, such as NO₂ or peroxyacetylnitrate, rendering too many false alarms for this approach to be viable. Therefore, two other techniques were evaluated. Single-photon ionization with nanosecond pulses in the vacuum ultraviolet is shown to produce only the parent ion, and is probably the most suitable choice. For 2,4-dinitrobenzene we find a limit of detection of about 40 ppb, for a signal to noise ratio of 3. This may be sufficient for land-mine detection, but improvement is likely with future work. Nonresonant multiphoton ionization in the ultraviolet with a femtosecond laser produces fragmentation but retains some parent ERC ion signal. The limit of detection is similar to that of single-photon ionization but it is harder to implement with lasers now commercially available. Future directions are outlined. PACS 07.07.Df; 33.80.Rv; 82.80.Ms; 82.80.Rt     

Observations on the spectral dependence andT/D isotope selectivity in the CO2 laser multiple-photon dissociation of trifluoromethane

Pulsed CO₂ laser multiple-photon dissociation of CTF₃ (v ₂ mode) bathed in argon and CDF₃, CHF₃ or CCl₄ is examined as a function of laser wavelength (9.2–9.6 m) and fluence. The dependence of the dissociation profile on wavelength is analyzed and comparisons are made to prior work. The single-stepT/D enrichment factor for infrared photolysis of trifluoromethane is measured; potential practical isotope separation is discussed. Pulsed infrared laser photolysis of CTF₃ (v ₅ mode) using a 12 m NH₃ laser is also attempted.     

Towards direct mass measurements of nobelium at SHIPTRAP

The Penning-trap mass spectrometer SHIPTRAP allows precision mass measurements of rare isotopes produced in fusion-evaporation reactions. In the first period of operation the masses of more than 50 neutron-deficient radionuclides have been measured. In this paper the perspectives for direct mass measurements of rare isotopes around nobelium are discussed and the achievable precision is addressed. The temporal stability of the magnetic field, an important issue for the long measurement times resulting from the low production rates, was investigated and the time-dependent uncertainty due to magnetic field fluctuations was determined. Based on the present performance direct mass measurements of nobelium isotopes are already feasible. With several technical improvements heavier elements between Z=102–105 will be in reach.