Laser spectroscopy of desorbing molecules

In this article the application of tunable dye lasers to desorption phenomena is illuminated. These lasers provide radiation continuously tunable from 105 nm in the vacuum ultraviolet to about 10 m in the mid-IR. By employing either laser induced fluorescence (LIF) or resonance enhanced multiphoton ionization (REMPI) spectroscopy almost all diatomic and many polyatomic molecules can be probed with the sensitivity required to detect desorbing molecules under UHV conditions. The spectral resolution of the lasers is sufficiently high that rotational state selectivity is achieved. Recent developments permit in addition the velocity distributions of molecules to be determined with internal quantum state resolution. Therefore very detailed information about the molecular dynamics has been obtained. In most experiments so far reactive recombinations off surfaces have been investigated. In this paper special emphasis will be given to the recombination of hydrogen on copper and palladium surfaces. For these systems very detailed data about the internal state populations at various surface temperatures have been obtained. The rotational cooling previously observed in molecular beam scattering has also been established for desorption. Strong vibrational excitation has been observed, which in the case of desorption from copper may be associated with the recombination dynamics, whereas for desorption of D₂ from Pd(100) a molecular precursor state might be responsible. By measuring the velocity distribution in each quantum state, the complete energetics of the desorbing molecules has been determined. Some first experiments on laser induced desorption with state selective detection of the desorbing molecules will also be discussed. Finally, making use of the polarization analysis of the signal, alignment effects in the desorption can be observed, permitting observation of molecular dynamics with a magnifying glass.Heisenberg fellow of the Deutsche Forschungsgemeinschaft     

Infrared absorption of H2 adsorbed on porous glass,silica gel,and MgO

Infrared absorption of the vibrational band of H₂ in the bulk is known to arise from overlap and quadrupolar interactions. For adsorbed H₂, in addition to intermolecular interactions, an interfacial mechanism of inducing absorption has been identified in porous Vycor glass. A large enhancement of the fundamental vibrational line (by a factor of 60) from the bulk H₂ (liquid) has been observed. The vibrational overtone absorption is similarly enhanced by 150. We discuss these results as well as infrared absorption measurements for H₂ on MgO and silica gels.     

Field emission energy distribution from adsorbate covered tungsten

We discuss the effect of various classes of adsorbates on the surface states and resonances known to produce structure in the field emission energy distribution from (100) tungsten. We show that it is the overlayer geometry which is of importance in determining whether or not the resonances and concomittant FEED structure persist in the presence of adsorbates. In particular, a c(2 × 2) krypton overlayer destroys the structure while a (1 × 1) gold overlayer does not.     

Raman diagnostics of heterogeneous chemical processes

The suitability of cw Raman spectroscopy for characterization of mass transport phenomena in connection with heterogeneous chemical processes is demonstrated for the example of the catalytic hydrogenation of acetylene. Temperature and concentration profiles in a model reactor were derived simultaneously from H₂ pure rotational lines and from the most intenseQ branches of C₂H₂ and of C₂H₄. The temperature dependence of the band contours has been considered; by careful calibration the systematic error of the derived concentration values is limited to less than 2%. The measurements allow the separation of the effects of thermal diffusion and of the reaction.     

Effects of post-desorption collisions on the energy distribution of SiCl molecules pulsed-laser desorbed from Cl-covered Si surfaces: Monte-Carlo simulations compared to experiments

Si surfaces covered with up to a monolayer of chlorine by exposure to a low chlorine pressure have been irradiated with nanosecond excimer-laser pulses at a fluence just large enough to melt the surface. Angle-resolved time-of-flight (TOF) distributions and surface temperatures have been measured as a function of chlorine dose between laser pulses. The TOF distributions can be fitted well by Maxwell-Boltzmann (MB) distributions for all coverages and at all desorption angles. With increasing coverage, the intensity and kinetic energy distributions become increasingly peaked along the surface normal. Monte-Carlo simulations of the effect of post-desorption collisions, occurring when many molecules are desorbed within a very short time, reproduce the experimental results quite well. It is shown that just a few collisions per molecule are sufficient to convert any initial desorption distribution into a MB one.     

The binding energy of CO on clean and sulfur covered platinum surfaces

The desorption of CO from clean Pt(111) and (100), and from the same surfaces with partial overlayers of sulfur, was studied by Thermal Desorption Spectroscopy. The method of desorption rate isotherms was employed for data analysis. The desorption of CO from the (111) surface and both surfaces with ordered sulfur overlayers can be described as a first order process with coverage dependent activation energies. The desorption of CO from the clean Pt(100) surface is complicated by the dynamic interaction of the molecule with a thermally activated change of platinum surface structure. On both platinum faces surface sulfur decreases the initial binding energy of CO. As the CO concentration increases, its binding energy decreases very rapidly. This is due to a repulsive interaction which exists between co-adsorbed species.     

Resonance CARS detection of SiC2 as reaction intermediate in IR laser synthesis of SiC from SiH4/hydrocarbon mixtures

Coherent anti-Stokes Raman Scattering has been employed to investigate gas-phase reactions between SiH₄ and small hydrocarbons leading to formation of SiC powder. SiC₂ has been identified as reaction intermediate, due to the occurrence of resonance enhanced CARS coupling vibrational leavels in the ground and first electronically excited state. The rich structure observed in the range 4480 Å<_AS<4650 Å is assigned to SiC₂ taking into account the cyclic geometry of this species and revising former data on electronic transitions.ENEA Guest     

Time-of-flight diagnostics of wavelength-dependent CO2 laser-induced desorption from condensed layers

Time-of-flight (TOF) diagnostics have been applied to study the interaction of CO₂ laser pulses with multilayers of D₂O, CH₃OH, CH₃F, CCl₄, and C₆H₅CHO condensed on different substrates (Ge, Ag, SiO₂). Maxwellian TOF distributions were fitted to the measured distributions. The TOF temperatures and the desorption yields show the same spectral features as do the respective ir absorption spectra. This indicates resonant heating by wavelength-dependent excitation of internal modes of the condensed molecules. Semilog plots of the desorption yield versus reciprocal TOF temperature exhibit Arrhenius behavior, as expected for a thermally activated process.     

Complete removal of paint from metal surface by ablation with a TEA CO2 laser

For high-speed metal surface cleaning, we applied TEA CO₂ laser pulses to ablate painted materials on metal surfaces and examined the efficiency of removal under different surface and irradiation conditions. Surfaces treated with a line-focused laser beam were analyzed with an energy dispersive X-ray analyzer and inspected with optical microscopic observation. Although paints were selectively ablated from the metal surface, the cleaning efficiency was found to depend on surface conditions of substrates. An application of a small amount of dimethyl formamide was effective for completely removing of resin without scorching the surface.     

Mechanism and speed of initial step of oxygen chemisorption-O2 on W

A direct first step in the mechanism for the initial oxidation of a polycrystalline tungsten surface, the catalyzed dissociation of O₂ on it, or the formation of WO _X by O₂ at intermediate temperatures is shown to occur in ∼10⁻¹³ s. Molecular beam experiments demonstrated that the reactivity was greater than 90%, the unreacted O₂ was substantially unaccommodated in translational energy to the surface temperature, and the reaction probability was nearly independent of surface temperature from 2800 to 415 K although there was a small increase at 415 K. The general conditions when no molecular surface precursor state contributes to the surface reactivity are discussed.     

Application of spontaneous Raman and Rayleigh scattering and 2D LIF for the characterization of a turbulent CH4/H2/N2 jet diffusion flame

4 /H₂/N₂ diffusion flame. Important aspects of the measuring technique, such as accuracy, cross talk between different Raman bands, and the correction procedure for background from laser-induced fluorescence are discussed. In addition, a 2D LIF and Rayleigh imaging system were used to study the structures of OH, CH, NO, and temperature distributions in the flame. A comparison between two different CH detection schemes is presented. A main goal of the investigations was a detailed and accurate characterization of the investigated flame as well as the study of experimental techniques. Joint pdfs of the temperature and major species concentrations were determined at nearly 100 measuring locations covering the complete flame. Parts of the results are presented in the paper in order to discuss effects of differential diffusion, flame extinction, and interaction between flow field and chemistry. The measured data sets which are available on the Internet are well suited for testing and validating mathematical flame models. Received: 8 July 1997/Revised version: 23 October 1997     

The velocity distribution of desorbing molecules: a simulation study

The distribution of velocity and directions of dissolved carbon dioxide, nitrogen and argon molecules escaping from liquid water into the vapour has been analysed. The distributions were found to agree well with those predicted from the thermal flux distribution and not with the recent theory for evaporation proposed by Phillips. Possible reasons for this are discussed.     

Terahertz absorption spectrum of D2O vapor

The absorption spectrum of D₂O vapor from 0.2 to 2.0 THz (6.7-67 cm⁻¹) which is associated with rotational modes was measured at one atmosphere using terahertz time-domain spectroscopy (THz-TDS). The linewidth and collisional dephasing times were measured for 26 pure rotational transitions in the ground vibrational state (0 0 0). The temperature dependence of the linewidth (Δν) behaves as Δν ∼ T^−3/4 and the linewidth decrease with increasing temperature is attributed to the 1/r⁶ force of interaction between colliding D₂O molecules.     

Adsorption-desorption kinetics of CO from clean and sulfur covered Ru(001)

The total uptake of CO, its adsorption kinetics and its desorption kinetics from clean and partially sulfur covered surfaces of the basal plane of ruthenium have been investigated. The method of desorption rate isotherms applied to the CO flash desorption spectra from these surfaces was used to evaluate the coverage dependence of the binding energy of CO as well as the effect of various levels of sulfur on this binding energy. Below a total surface concentration of 1 adsorbate atom per 3 surface Ru atoms, the binding energy and sticking probability of CO on the clean and sulfur covered surfaces are the same. Above this concentration of total adsorbates, the adsorption kinetics is the same on all surfaces studied, the binding energy decreases linearly with CO coverage while the magnitude of the decrease increases with sulfur coverage. The total uptake of CO depends on the amount of preadsorbed sulfur. At low coverages of sulfur, total CO uptake is effected by the excluded volume of sulfur. At higher coverages of sulfur (approaching $\text{1}\text{2}$ the maximum sulfur concentration on the clean surface) the site requirements of sulfur limits the amount of CO that can adsorb on the remaining surface, to the quantity of 1 adsorbate atom per 2 Ru atoms.     

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.     

The fundamental band ν2 of D2CO

The ν₂ band of D₂¹³CO in the region of 1570-1760 cm⁻¹ has been analyzed with high accuracy. The limits of the quantum numbers J and K_a are 50 and 16, respectively. The number of the assigned transitions is 3858. A local anharmonic resonance ν₂/2ν₄ at K_a =  8-12 was observed. The Watson’s A-reduced Hamiltonian and anharmonic resonance term were fitted to the observed transitions. The fit resulted in the band center and rotational parameters of the ν₂ band as well as the effective parameters for the 2ν₄ band and anharmonic resonance parameter. The rms deviation of the transitions in the ν₂ band was 0.000364 cm⁻¹.     

The ground state rotational spectrum of SO2F2

The analysis of the ground state rotational spectrum of SO₂F₂ [K. Sarka, J. Demaison, L. Margulès, I. Merke, N. Heineking, H. Bürger, H. Ruland, J. Mol. Spectrosc. 200 (2000) 55] has been performed with the Watson’s Hamiltonian up to sextic terms but shows some limits due to the A and S reductions. Since SO₂F₂ is a quasi-spherical top, it can also be regarded as derived from an hypothetical XY₄ molecule. Thus we have developed a new tensorial formalism in the O(3)⊃T_d⊃C_2v group chain (M. Rotger, V. Boudon, M. Loëte, J. Mol. Spectrosc. 216 (2002) 297]. We test it on the ground state of this molecule using the same experimental data (10 GHz-1 THz region, J up to 99). Both fits are comparable even if the formalisms are slightly different. This paper intends to establish a link between the classical approach and the tensorial formalism. In particular, our tensorial parameters at a given order of the development are related to the usual ones. Programs for spectrum simulation and fit using these methods are named C_2vTDS. They are freely available at the URL:http://www.u-bourgogne.fr/LPUB/c2vTDS.html.     

Exhaust-gas imaging via planar laser- induced fluorescence of sulfur dioxide

The potential use of planar laser-induced fluorescence (PLIF) of sulfur dioxide (SO₂) for visualization of exhaust-gas distributions is outlined and demonstrated. Strong absorption features in the UV spectral range allow excitation of SO₂ with the fourth harmonic of a Nd:YAG laser at 266 nm. Fluorescence emissions are mostly red-shifted and can be easily detected in single-shot imaging arrangements with a good signal-to-noise ratio. This study uses a premixed methane/air flame that is doped with SO₂ to demonstrate the technique. The signal strength has a pronounced temperature dependence for excitation at 266 nm. Received: 14 January 2002 / Revised version: 30 January 2002 / Published online: 14 March 2002