Femtosecond time-resolved laser-induced desorption of positive ions from MgO

We have used the pump-probe technique to measure the photostimulated positive ion yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the ion yield from UV femtosecond irradiated MgO depends critically on the laser pulse delay, (t, in two-pulse experiments. In single-pulse experiments, excitation of MgO produces a variety of ions including Mg⁺, MgO⁺, and a significant yield of H⁺. In contrast, if the femtosecond laser pulse is split into two sub-threshold beams and then recombined with a variable time delay, the ion yield may be drastically altered depending on the delay between pulses. The Mg⁺ desorption yield displays three distinct lifetimes and persists for laser delays of over 100 ps. A pulse delay of only (t=500 fs nearly eliminates ion desorption except for Mg⁺. The use of a pair of delayed femtosecond laser pulses can thus control the species of the desorbed ion. The mechanism for femtosecond laser desorption is clearly different from nanosecond laser desorption. We hypothesize that the creation of electron-hole pairs by nonresonant two-photon excitation contributes to the ultrafast desorption mechanism.     

Probing the mechanisms of ambient ionization by laser-induced fluorescence spectroscopy

The ionization mechanisms of several atmospheric pressure ion sources based on desorption and ionization of samples deposited on a surface were studied. Home-built desorption electrospray ionization (DESI), laserspray ionization (LSI), and atmospheric pressure matrix-assisted laser desorption/ionization (AP-MALDI) sources were characterized using low-molecular-weight compounds, in particular fluorescent dyes. Detection of the desorbed and ionized species was performed by laser-induced fluorescence and ion cyclotron resonance mass spectrometry. The dependences of the signal intensities on various experimental parameters were studied. The data obtained reveals common features, such as formation of solvated species and clusters in the ionization processes, in all of the techniques considered.     

Analytical laser induced liquid beam desorption mass spectrometry of protonated amino acids and their non-covalently bound aggregates

We have used analytical laser induced liquid beam desorption in combination with high resolution mass spectrometry ( m/Δm≥ 1000) for the study of protonated amino acids (ornithine, citrulline, lysine, arginine) and their non-covalently bound complexes in the gas phase desorbed from water solutions. We report studies in which the desorption mechanism has been investigated. The results imply that biomolecule desorption at our conditions is a single step process involving laser heating of the solvent above its supercritical temperature, a rapid expansion, ion recombination and finally isolation and desorption of only a small fraction of preformed ions and charged aggregates. In addition, we report an investigation of the aqueous solution concentration and pH-dependence of the laser induced desorption of protonated species (monomers and dimers). The experimental findings suggest that the desorption process depends critically upon the proton affinity of the molecules, the concentration of other ions, and of the pH value of the solution. Therefore the ion concentrations measured in the gas phase very likely reflect solution properties (equilibrium concentrations). Arginine self-assembles large non-covalent singly protonated multimers (n = 1...8) when sampled by IR laser induced water beam desorption mass spectrometry. The structures of these aggregates may resemble those of the solid state and may be preformed in solution prior to desorption. A desorption of mixtures of amino acids in water solution enabled us to study (mixed) protonated dimers, one of the various applications of the present technique. Reasons for preferred dimerization - leading to simple cases of molecular recognition - as well as less preferred binding is discussed in terms of the number of specific H-bonds that can be established in the clusters.     

Prospects for Further Development of Self-Heated Lasers on the Self-Contained Transitions of a Copper Atom

An analysis of the causes restricting the frequency–energy characteristics of a copper vapor laser is carried out. The principal cause of the restriction is shown to be the high deexcitation rate of the higher laser levels into the ionized state. This involves a strong increase in the expenditures of energy for the population inversion with a rise in the electron density before the pulse and a high $Q$ factor of the discharge circuit at the end of the exciting pulse. The high Q factor of the discharge circuit is responsible for the oscillatory process of energy dissipation within the time spacing between pulses. This energy is stored in the reactive component of impedance of the discharge tube during the excitation pulse. The oscillatory dissipation defines a slow relaxation of the lower laser levels within the time spacing between the pulses. Analysis of the conditions of population inversion formation in a copper vapor laser shows that the active medium should be pumped in a two-pulse excitation mode to realize the energy potential of the laser of 1–2 kW/liter. The advantages of such an excitation mode over the traditional single-pulse excitation are confirmed.     

Isotope effects in electron impact desorption of CO and O2 adsorbed on the (110) plane of tungsten

Results on the isotope effect for total and ionic desorption cross sections in the electron impact desorption of various binding states of CO on the (110) plane of tungsten, and of oxygen on this plane are presented and discussed. It is shown that the observations allow a dissection of cross sections into excitation cross sections and escape probabilities, and that the latter can be used to estimate lifetimes of excited or ionic states. It is found that excitation cross sections for total desorption are of the order of 10^?16–10^?17 cm², but seem to be significantly smaller in some cases for excitation to ionic states, suggesting that different excitations are involved. In all cases examined here the isotope effect for total desorption is much smaller than for ion production. This can be explained by the fact that ion lifetimes are somewhat shorter than those of excited neutrals. Lifetimes are estimated, in the cases examined, to be of the order of 10^?14s.     

Laser-induced vibrational excitation and desorption in the Cs/Cu(1 1 1) and Na/Cu(1 1 1) systems

The Cs/Cu(1 1 1) and Na/Cu(1 1 1) systems exhibit a transient excited electronic state localized on the adsorbate. Photo-excitation of this state triggers a motion of the alkali adsorbate away from the surface, leading to vibrational excitation of the adsorbate and possibly to desorption. A theoretical study of these photo-induced processes in the case of an exciting fs laser pulse is reported, based on a time-dependent approach of the adsorbate motion. The mean energy transfer from the laser photon energy to the adsorbate motion is shown to be weak, about 1% of the photon energy. Correspondingly, the vibrational excitation to high lying levels is very weak as well as the desorption process. The initial electronic state of the photo-induced process belongs to a continuum and vibrational excitation and desorption are found to vary rapidly with the energy of the initial electronic state. Initial vibrational excitation of the alkali adsorbate is also found to efficiently favour the desorption process, leading to a drastic variation of the desorption probability with the vibrational temperature of the adsorbate. The present results for the two systems are discussed and compared, in connection with available experimental data on these systems and on similar ones.     

Photoionization and Dissociative Photoionization Study of Cholesterol by IR Laser Desorption/Tunable Synchrotron VUV Photoionization Mass Spectrometr

介绍了一种将红外激光解吸/真空紫外光电离质谱技术应用于分析胆固醇的新方法. 由于近阈值单光子电离作用,可以在低能量下只产生纯净的胆固醇分子离子峰;增加光子能量则可以使碎片离子峰大量出现. 为了验证碎片离子的归属,利用商用高分辨电子轰击电离-飞行时间质谱仪分析并指认了胆固醇主要的碎片峰. 此外,采用量子化学从头算的方法研究了胆固醇母体离子和碎片构型,并讨论了部分主要的光解离机理     

Isotope effects in electron impact desorption of CO and O2 adsorbed on the (110) plane of tungsten

Results on the isotope effect for total and ionic desorption cross sections in the electron impact desorption of various binding states of CO on the (110) plane of tungsten, and of oxygen on this plane are presented and discussed. It is shown that the observations allow a dissection of cross sections into excitation cross sections and escape probabilities, and that the latter can be used to estimate lifetimes of excited or ionic states. It is found that excitation cross sections for total desorption are of the order of 10⁻¹⁶–10⁻¹⁷ cm², but seem to be significantly smaller in some cases for excitation to ionic states, suggesting that different excitations are involved. In all cases examined here the isotope effect for total desorption is much smaller than for ion production. This can be explained by the fact that ion lifetimes are somewhat shorter than those of excited neutrals. Lifetimes are estimated, in the cases examined, to be of the order of 10⁻¹⁴s.     

Electron and photon stimulated desorption of positive ions from alkali halide surfaces

We have observed desorption of positive ions from alkali halides stimulated by low energy electron and photon bombardment. Our experiments include the first measurements of electron stimulated desorption (ESD) of Na⁺ from NaCl and the first measurements of photon stimulated desorption (PSD) of positive ions from NaCl and LiF. The energy dependence data indicate that the initial onset for Na⁺ ejection by ESD occurs at the excitation threshold of the Cl(3s) core level. Similarly for the PSD of positive ions from NaCl and LiF we can relate incident photon beam energy dependent ion yields with the production of substrate core holes. The data provide insight into the mode of initial energy transfer to the solid which leads to desorption. ESD and PSD ion yields were measured to be on the order of 10^?7 ions per incident electron or photon.     

Non-linear photo-induced desorption of GaP

Laser-induced desorption of P from GaP at various photon energies near the absorption edge has been measured. The desorption yield is found to start increasing above a certain threshold laser fluence, of which the dependence on the photon energy exhibits a sharp dip near the indirect band gap besides a gradually decreasing component from the indirect band gap to the direct band gap energy. The sharp dip is ascribed to desorption induced by dense excitation of the surface states.     

Laser-induced desorption and etching processes on chlorinated Cu and solid CuCl surfaces

Time-resolved mass spectrometry is used to study the desorbed species due to laser-induced etching of a solid CuCl and a chlorinated Cu surface. The observed desorption threshold, mass distribution and kinetic energies of the desorbed atoms and molecules at 355 and 532 nm radiation show that the laser-induced etching process is not simply thermal evaporation. It is suggested that competing nonthermal mechanisms due to electronic excitations may be very important in laser-induced desorption and etching. These processes are different for a solid CuCl and a chlorinated Cu surface. For laser-induced etching of Cu surfaces, chlorination of Cu is essential; however, formation of stoichiometric CuCl is not necessary. Excess Cu in the surface layer is responsible for the observed different etching behavior of a chlorinated Cu and a solid CuCl surface. The effect of laser radiation on these surfaces and possible etching mechanisms are discussed based on the experimental observations.     

Photodesorption of weakly bound molecules

A recently reported lineshape function which specifically applies to the problem of one-photon photodesorption is used to perform model calculations. The expected efficiency and timescale for such a process is obtained. Molecules physisorbed on solid surfaces may desorb when vibrational energy from laser excitation leaks into the surface-adsorbate bond. Using phenomenological rate constants for desorption, quenching and dephasing mechanisms, a simple expression for surface coverage as a function of laser and molecular parameters is obtained. Analogy is drawn to the vibrational predissociation of Van der Waals molecules, to which this model has been previously applied. Sample experimental sytems are examined and calculations are made to explore the feasibility and range of the photodesorption technique. Observable effects are calculated, even for low-power laser parameters and fast quenching rates. Conversely, the lineshape formula provides a method for extracting desorption and quenching rates from experimental data. Extension of the model to other systems is discussed.     

Laser-induced gas-surface interactions

Chemical reactions in homogeneous systems activated by laser radiation have been extensively investigated for more than a decade. The applications of lasers to promote gas-surface interactions have just been realized in recent years. The purpose of this paper is to examine the fundamental processes involved in laser-induced gas-surface chemical interactions. Specifically, the photon-enhanced adsorption, adsorbate-adsorbate and adsorbate-solid reactions, product formation and desorption processes are discussed in detail. The dynamic processes involved in photoexcitation of the electronic and vibrational states, the energy transfer and relaxation in competition with chemical interactions are considered. These include both single and multiple photon adsorption, and fundamental and overtone transitions in the excitation process, and inter- and intra-molecular energy transfer, and coupling with phonons, electron-hole pairs and surface plasmons in the energy relaxation process. Many current experimental and theoretical studies on the subject are reviewed and discussed with the goal of clarifying the relative importance of the surface interaction steps and relating the resulting concepts to the experimentally observed phenomena. Among the many gas-solid systems that have been investigated, there has been more extensive use of CO adsorbed on metals, and SF₆ and XeF₂ interactions with silicon as examples to illustrate the many facets of the electronically and vibrationally activated surface processes. Results on IR laser stimulated desorption of C₅H₅N and C₅D₅N molecules from various solid surfaces are also presented. It is clearly shown that rapid intermolecular energy exchange and molecule to surface energy transfer can have important effects on photodesorption cross sections and isotope selectivities. It is concluded that utilization of lasers in gas-surface studies not only can provide fundamental insight into the mechanism and dynamics involved in heterogeneous interactions, but also offer the possibility for technical innovation for practical applications.     

Study of the sputtering of adsorbates by low energy ions (O on Ni)

Sputtering or ion impact desorption of adsorbed layers has been studied by low energy ion scattering and model calculations. For adsorption of a monolayer or less (e.g. oxygen on nickel) the desorption by ions can be readily observed by He⁺ ion scattering from the development of the adsorbate and substrate signal as a function of time. Desorption cross sections for Ne⁺ and He⁺ ions in the energy range from 500 eV to 1600 eV are given. These results are compared with the model calculations and the influence of various parameters can be studied by this comparison. The contribution of different processes to the sputtering mechanism is discussed.     

Photoablation of polyurethane films using UV laser pulses

Pulsed ultraviolet laser ablation of two polyurethane films has been studied in terms of ablation rate behaviour and time-of-flight mass spectroscopy of the positively charged photofragments. Three excimer laser wavelengths (193, 248 and 308 nm; 17–30 ns pulse duration) and short-pulse laser system (pulse duration 500 fs or 5 ps, at 248 nm) were employed. The results of the influence of energy fluence on the ablation rate are tested against other photoablation models and a table of fitted physical constants is presented. The upper limit of the mean activation energy for desorption is found to be considerably lower than the energy required to break single covalent bonds. The mass analysis of the positively charged species produced during the photoablation process provides valuable insight into the photofragmentation mechanism.     

Desorption of an organic conducting polymer by soft X-ray radiation created by a femtosecond laser

The possibility of the desorption of complicated molecular complexes by soft X rays resulting from a solid target irradiated by a single sharply focused femtosecond laser pulse with an energy of several millijoules has been experimentally demonstrated for polyaniline, which is an organic conducting polymer. X-ray desorption and photodesorption of polyaniline by femtosecond laser pulses have been compared using a time-of-flight mass spectrometer. The results provide the possibility of studying surfaces with spatial nanoresolution and high elemental (chemical) selectivity, as well as observing the photodesorption with a high temporal resolution.     

Auger-electron-ion coincidence study of photon-stimulated ion desorption for condensed acetonitrile

Auger-electron-photoion coincidence (AEPICO) studies of photon-stimulated ion desorption (PSID) for condensed acetonitrile induced by carbon core excitation have been performed to elucidate the desorption mechanism related to the Auger process. We have detected only the H⁺ ion in AEPICO spectra. The total ion yield spectrum divided by the total electron yield shows that the desorption efficiency is largely increased at the resonant excitation to C---H*. We have also measured the Auger electron spectrum and the AEPICO yield spectrum at the C---H* excitation. The AEPICO yield spectrum shows enhancement at 245–250 eV electron energy. This seems to be related to the spectator resonant Auger stimulated ion desorption. That is, H⁺ desorption is enhanced due to a two-hole-one-electron state at which the electron is in an anti-bonding C---H* orbital and the two holes can be in a 1π bonding orbital localized on the ---CH₃ group. We have also measured similar spectra for other resonant excitation (π*_CN, σ*_CC, σ*_CN). The results are discussed in connection with the bonding/anti-bonding character and localized character of the excited state.     

Ultrafast and nanosecond laser-induced desorption of positive ions from lithium fluoride single crystals

We compare desorption of positive ions from lithium fluoride single crystals following pulsed laser excitation using either femtosecond (180 fs, 265 nm) or nanosecond (3 ns, 266 nm) sources. Following optical excitation, desorbed ions are mass analyzed using standard time-of-flight techniques. Several important differences between nanosecond and femtosecond excitation are revealed. Femtosecond excitation produces higher kinetic energy Li⁺ than does nanosecond excitation (10 eV vs. 5 eV) while nanosecond excitation yields significant quantities of impurity ions Na⁺ and K⁺, in addition to efficient Li⁺ emission. The Li⁺ desorption threshold is similar for both laser sources. This similarity is a surprising result, as sub-bandgap nanosecond pulses are only likely to excite defect states efficiently (via linear excitation), while the ultrahigh peak-power femtosecond pulses could in principle induce multiphoton and avalanche excitation. Femtosecond excitation results in much less complicated time-of-flight spectra, as predominantly Li⁺ is detected with some H⁺ also observed. We have measured the Li⁺ yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the majority of the Li⁺ yield decays rapidly, largely within the fs pulse duration. However, a weak but measurable decay component of approximately 2 ps is indicated.