Laser-induced fluorescence study of fast desorption of ground-state K atoms from potassium halides excited by synchrotron radiation

The nanosecond desorption of ground-state K atoms from potassium halides was investigated for the first time using a laser-induced fluorescence method with synchrotron radiation and laser pulses. It was found that the desorption consists of a nanosecond component and a slow one of > 180 ns response time. The fast desorption is several orders of magnitude faster than existing results for the time response of ground-state alkali desorption. Therefore, the fast desorption of ground-state alkali atoms cannot be interpreted in terms of the existing mechanisms based on thermal processes and requires a new desorption model. We suggest that the lattice instability due to electronic excitation in the surface layer may play an important role in the fast desorption of ground-state alkali atoms.     

Leakage of O2 precursor molecules from inert hydrogen islands on a Pt(111) surface

We have observed, using infrared spectroscopy, that the precursor-mediated O2 chemisorption on the clean and the partially hydrogen-covered Pt(111) surfaces exhibits opposite temperature dependencies above the temperature for stable O2 physisorption. While the chemisorption probability on the clean surface increases with increasing temperature due to thermal activation of the precursor, it decreases on the partially hydrogen-covered surface which we suggest is due to a general loss of the mobile precursor molecules by thermal desorption from chemically inert hydrogen islands.     

Photo- and thermodesorption of helium on Pt(111)

In a detailed study of thermal desorption of monolayers of both 4He and 3He adsorbed on Pt(111) (binding energy about 9 meV), we have observed photodesorption induced by the blackbody radiation from a room temperature environment. This process proceeds independently of the thermal desorption. Theoretical treatments of both thermal and photodesorption are given and agree very well with the data in all important aspects. We conclude that the photodesorption is due to direct coupling of photons to the adsorbate.     

Thermal desorption of large molecules from solid surfaces

We use molecular-dynamics simulations and importance sampling to obtain transition-state-theory rate constants for thermal desorption of an n-alkane series from Au(111). We find that the binding of a large molecule to a solid surface involves different types of local minima. The preexponential factors increase with increasing chain length and can be substantially larger than typical estimates for small molecules. Our results match recent experimental studies and indicate that a proper treatment of conformational isomerism and entropy, heretofore not found in coarse-grained models, is essential to quantitatively describe the thermal desorption of large molecules from solid surfaces.     

Experimental and theoretical studies of linear polyatomic molecules on surfaces of low symmetry: C2N2- on Pt(110)

The adsorption and surface dissociation of C₂N₂ on Pt(110), and the desorption kinetics of cyanide adlayers have been studied by LEED, Auger spectroscopy, and thermal desorption. The unusual adsorption kinetics which are accompanied by a (1 × 2) → (1 × 1) change in the surface periodicity are discussed in terms of absolute rate theory. The desorption process is modelled using 2D Monte Carlo and 1D analytical methods; these calculations indicate that the adlayer is only partly equilibrated — a conclusion which is confirmed by the results of CO coadsorption experiments. Values are deduced for the desorption parameters which suggest that the CN molecule is multiply bonded to the Pt surface.     

Diffusion effects on thermal desorption spectra of hydrogen from (111) surfaces of diamond-type crystals

We study the thermal desorption of atoms located in subsurface interstitial sites at the (111) surface of crystals with a diamond-type structure. From these sites they may either desorb or diffuse deeper into the crystal. A set of master equations is set up to describe the resulting random walk problem, and its solution yields both the desorption rate and total desorbed amount, as a function of time for constant temperature thermal desorption, or of temperature for flash desorption with a constant heating rate. Unequal values of the desorption and diffusion probabilities are allowed and the effect of initial occupation of deeper interstitial sites as well, is considered. In the latter case the desorption rate curve shows a double peak when the probabilities favour desorption, and in all cases a distinct long time or high temperature tail of the peak is found to result from diffusion. Based on this study, a model of H adsorption on Si(111) is presented and shown to explain several features of the experimental results of Schulze and Henzler.     

Glycine on Pt(111): a TDS and XPS study

The adsorption and desorption of in situ deposited glycine on Pt(111) were investigated with thermal desorption spectroscopy (TDS) and X-ray photoelectron spectroscopy (XPS). Glycine adsorbs intact on Pt(111) at all coverages at temperatures below 250 K. The collected results suggest that the glycine molecules adsorb predominantly in the zwitterionic state both in the first monolayer and in multilayers. Upon heating, intact molecules start to desorb from multilayers around 325 K. The second (and possibly third) layer(s) are somewhat more strongly bound than the subsequent layers. The multilayer desorption follows zero order kinetics with an activation energy of 0.87 eV molecule⁻¹. From the first saturated monolayer approximately half of the molecules desorbs intact with a desorption peak at 360 K, while the other half dissociates before desorption. Below 0.25 monolayer all molecules dissociate upon heating. The dissociation reactions lead to H₂, CO₂, and H₂O desorption around 375 K and CO desorption around 450 K. This is well below the reported gas phase decomposition temperature of glycine, but well above the thermal desorption temperatures of the individual H₂, CO₂, and H₂O species on Pt(111), i.e. the dissociation is catalyzed by the surface and H₂, CO₂, and H₂O immediately desorb upon dissociation. For temperatures above 500 K the remaining residues of the dissociated molecules undergo a series of reactions leading to desorption of, for example, H₂CN, N₂ and C₂N₂, leaving only carbon left on the surface at 900 K. Comparison with previously reported studies of this system show substantial agreement but also distinct differences.     

Thermal desorption states of C<Subscript>60</Subscript> fullerene molecules in polymer matrices

Polymer-C₆₀ fullerene composite coatings are studied using thermal desorption mass spectrometry. It is found that thermal desorption spectra of C₆₀ fullerene molecules can exhibit several resolved peaks (at a specified heating rate) corresponding to thermal desorption states. The relative intensity of the thermal desorption peaks depends on the procedure used for preparing the composite coatings, in particular, on the time of sedimentation of the polymer-fullerene suspension. The occurrence of different stages in thermally stimulated desorption of C₆₀ fullerene molecules is explained by the fact that the fullerene molecules can exist in several phase states characterized by different densities and degrees of ordering in the polymer matrix.     

Chemisorption and rotational epitaxy of lithium on Ru(001)

Rotational epitaxy of an overlayer along a non-symmetry direction of the substrate has been observed as a mechanism for the accommodation of lattice mismatch in rigid thin films. We have examined the adsorption and rotational epitaxy of Li on the Ru(001) surface using low energy electron diffraction and thermal desorption spectroscopy. At 80 K, commensurate (2 × 2) and (√3 × √3)R30° phases were observed at coverages below 0.33 monolayer. At higher coverages, the Li layer orientation rotates relative to the substrate as the interatomic spacing of the layer is compressed. This behavior is qualitatively similar to that observed for Na on Ru(001), but differences were observed which may suggest that Li overlayers are less rigid than Na overlayers.     

Coverage dependent desorption measurements of COCu(001)

We report time-resolved electron energy loss spectroscopy measurements of the coverage-dependent kinetic parameters for the thermal desorption of CO from Cu(001). Large, parallel increases in the activation energy for desorption and desorption prefactor are observed as a function of coverage. The activation energy away from zero coverage differs significantly from the measured isosteric heat of adsorption. The significance of these results is discussed in terms of applicable statistical models. We deduce the existence of an unusual temperature dependence in the adsorbate configurational entropy.     

Interaction kinetics of atoms and molecules on carbon nanotube surfaces

We review recent experimental investigations of the interaction of gases with the surface of single-wall carbon nanotube bundles. We discuss thermal desorption spectra of both non-polar and polar adsorbates for low and high coverage. We show experimental results for diffusion processes of Xe along and within carbon nanotube bucky paper material, which is consistent with a recently proposed coupled desorption diffusion (CDD) model. We further discuss details of the interaction of ammonia with carbon nanotube surfaces, including the experimental investigation of the influence of adsorbed ammonia on the electrical transport properties of carbon nanotubes under ultra-high vacuum conditions.     

Water vapor desorption and adsorbent regeneration for air conditioning unit using pulsed corona plasma

The dehumidifying action of a dehumidifier or air conditioner was employed to achieve a comfortable and desirable indoor comfort. Water vapor adsorbed on an adsorbent substance needs to be regenerated when the water vapor exceeds the adsorption capacity. The conventional process for adsorbent regeneration or moisture desorption uses the heat by means of the electric heater. In the present study, the water vapor desorption from the adsorbent material was investigated using a pulsed corona plasma for possible replacement of the electric heater. The water vapor desorption for a given power (defined as desorption efficiency) using the pulsed corona plasma was found to be superior over conventional thermal desorption. The gradient of desorption (desorption rate) was found to be significantly higher for plasma desorption, so that faster desorption can be achieved without excessive gas heating. In addition, the plasma desorption was not affected by the initial moisture content in an indoor environment, which leads to more economical, controllable, and flexible air conditioning system.     

Thermal desorption spectra of chemisorbed atoms and molecules with lateral interactions and finite mobility: Nondissociatively adsorbed molecules

A model of thermal flash desorption of interacting chemisorbed atoms and molecules from a crystal surface is developed. The possibility of adatom diffusion along the surface is taken into account, but thermal equilibrium of the adatom system during the desorption process is not assumed. The whole range of adsorbate mobilities, including absolutely immobile species as well as adsorbates in thermal equilibrium, is investigated. The result is obtained in the form of a chain of differential equations for correlation functions of occupation numbers which is solved in various approximations. The numerical results differ from the results of previous calculations and are in better agreement with the experiments. The experimental thermal desorption spectrum of CO on W(210) is satisfactorily reproduced.     

Vibrational spectra of ammonia chemisorbed on platinum (111): I. Identification of chemisorbed states

Ammonia chemisorption on Pt(111) has been studied with high resolution electron energy loss spectroscopy (EELS), combined with thermal desorption spectroscopy (TDS). We detect two distinct molecular states of ammonia at different coverages. Near saturation monolayer coverage, ammonia is weakly chemisorbed (ΔH_ads ～ 9 kcal mol^?1) and coordinated to the metal surface via the nitrogen atom. The vibrational frequencies are shifted from the gas phase values, but not as strongly perturbed as in stable platinum-ammine complexes. Below 40% saturation coverage, a new molecular ammonia state is detected, which has a distinct vibrational and thermal desorption spectrum. This state has a considerably reduced ν(PtN) intensity, and the other frequencies are closer to those in solid ammonia, indicating a weaker interaction with the Pt surface. The thermal desorption spectrum of this lower coverage state is broad, from 160 to 450 K, and coverage dependent. Conversion between the two molecular states appears to be only a function of coverage. We propose that the two molecular states have different adsorption sites, and convert from one form to the other as the coverage is changed. No evidence is found for significant dissociation of ammonia on the Pt surface. At very low temperatures (100 K), solid ammonia multilayers may be grown.     

Interaction of cesium and oxygen on W(110): I. Cesium adsorption on oxygenated and oxidized W(110)

Cesium adsorption on oxygenated and oxidized W(110) is studied by Auger electron spectroscopy, LEED, thermal desorption and work function measurements. For oxygen coverages up to 1.5 × 10¹⁵ cm^?2 (oxygenated surface), preadsorbed oxygen lowers the cesiated work function minimum, the lowest (～1 eV) being obtained on a two-dimensional oxide structure with 1.4 × 10¹⁵ oxygen atoms per cm². Thermal desorption spectra of neutral cesium show that the oxygen adlayer increases the cesium desorption energy in the limit of small cesium coverages, by the same amount as it increases the substrate work function. Cesium adsorption destroys the p(2 × 1) and p(2 × 2) oxygen structures, but the 2D-oxide structure is left nearly unchanged. Beyond 1.5 × 10¹⁵ cm^?2 (oxidized surface), the work function minimum rises very rapidly with the oxygen coverage, as tungsten oxides begin to form. On bulk tungsten oxide layers, cesium appears to diffuse into the oxide, possibly forming a cesium tungsten bronze, characterized by a new desorption state. The thermal stability of the 2D-oxide structure on W(110) and the facetting of less dense tungsten planes suggest a way to achieve stable low work functions of interest in thermionic energy conversion applications.     

The co-adsorption of oxygen and hydrogen on Rh(111)

The co-adsorption of oxygen and hydrogen on Rh(111) at temperatures below 140 K has been studied by thermal desorption mass spectrometry, Auger electron spectroscopy, and lowenergy electron diffraction. The co-adsorption phenomena observed were dependent upon the sequence of adsorption in preparing the co-adsorbed overlayer. It has been found that oxygen extensively blocks sites for subsequent hydrogen adsorption and that the interaction splits the hydrogen thermal desorption into two states. The capacity of the oxygenated Rh(111) surface for hydrogen adsorption is very sensitive to the structure of the oxygen overlayer, with a disordered oxygen layer exhibiting the lowest capacity for hydrogen chemisorption. Studies with hydrogen pre-adsorption indicate that a hydrogen layer suppresses completely the formation of ordered oxygen superstructures as well as O₂ desorption above 800 K. This occurs with only a 20% reduction in total oxygen coverage as measured by Auger spectroscopy.     

Benzene and thiophene formation from acetylene on sulfided Pd(111) studied by LITD/FTMS

We report the first laser-induced thermal desorption (LITD) studies of acetylene on Pd(111). LITD coupled with Fourier transform mass spectrometry (FTMS) probes the surface molecular composition. Our results show simultaneous formation of thiophene and benzene at 120 K after a 6 L dose of acetylene at 80 K on a Pd(111) surface with 0.06 ML of sulfur. Simultaneous formation implies that formation of the C₄H₄ intermediate is the slow step in the formation of both cyclic products. The relative amounts of thiophene and benzene observed with LITD/FTMS are comparable, while thermal desorption spectroscopy (TDS) yields integrated thiophene signals that are < 2% as intense as for benzene. This indicates that thiophene primarily decomposes upon heating. Low coverage (0.5 L) results confirm reports that the presence of sulfur enhances benzene production.     

Chemisorption and reaction of NH3 on Ni(111)

The chemisorption of ammonia on Ni(111) has been investigated using LEED, thermal desorption, and angle-resolved photoemission. For exposures at 200 K, thermal desorption shows a coverage-dependent binding energy associated with dipole-dipole interactions. A (2 × 2) LEED pattern occurs at 2–4 L exposure. Time dependence of the LEED pattern and changes in the thermal desorption induced by the LEED beam indicate that the (2 × 2) pattern is due to a stable intermediate decomposition species. Using synchrotron radiation photoemission all three valence orbitals of ammonia have been observed for the first time. The energies of the ammonia-induced features in the photoemission (?22.0, ?11.0 and ?6.7 eV below the Fermi energy) and the observed symmatries positively identify the absorbed species as molecular ammonia. Additional structure observed in the photoemission spectra after electron bombardment is associated with the stable adsorbed intermediate.     

Coadsorption of cyanogen and potassium on Pt(111)

The coadsorption of potassium and cyanogen on Pt(111) has been studied by thermal desorption spectroscopy. A new feature in the cyanogen desorption is identified at 363 K, 30 K above the desorption temperature for the molecular state of cyanogen on clean Pt(111). The potassium/cyanogen interaction which leads to the new desorption feature has a reasonably well defined 1 : 1 stoichiometry.     

Hydrogen adsorption on a clean palladium ribbon; Thermal desorption and work function measurements

The adsorption of hydrogen on a palladium ribbon has been studied by thermal desorption and work function measurements. It has been established that several heating cycles of the sample covered with hydrogen, up to 700 K lead to the repeated appearance of hydrogen thermal desorption peaks. Analogous experiments of adsorption and repeated heating cycles up to 700 K have shown work function changes decrease to zero as a result of heating and an increase again almost up to the initial value following cooling, in a much shorter time than that required for adsorption. The experimental results show that only a small part of the adsorbed hydrogen is desorbed in the temperature range of the thermal desorption peak. The major part of adsorbed hydrogen penetrates below the surface which leads to a nonequilibium increase of the bulk concentration.