Correlated angular and quantum state-resolved CO2 scattering dynamics at the gas-liquid interface

Molecular beam scattering dynamics at the gas-liquid interface are investigated for CO2 (E(inc) = 10.6(8) kcal/mol) impinging on liquid perfluoropolyether (PFPE), with quantum state (v, J) populations measured as a function of incident (theta(inc)) and final (theta(scat)) scattering angles. The internal state distributions are well-characterized for both normal and grazing incident angles by a two-component Boltzmann model for trapping desorption (TD) and impulsive scattering (IS) at rotational temperatures T(rot)(TD/IS), where the fractional TD probability for CO2 on the perfluorinated surface is denoted by TD and IS densities (rho) as alpha = rhoTD/(rhoTD + rhoIS). On the basis of an assumed cos(theta(scat)) scattering behavior for the TD flux component, the angular dependence of the IS flux at normal incidence (theta(inc) = 0 degrees) is surprisingly well-modeled by a simple cos(n)(theta(scat)) distribution with n = 1.0 +/- 0.2, while glancing incident angles (theta(inc) = 30 degrees, 45 degrees, and 60 degrees) result in lobular angular IS distributions scattered preferentially in the forward direction. This trend is also corroborated in the TD fraction alpha, which decreases rapidly under non-normal incident conditions as a function of backward versus forward scattering direction. Furthermore, the extent of rotational excitation in the IS channel increases dramatically with increasing angle of incidence, consistent with an increasing rotational torque due to surface roughness at the gas-liquid interface.     

Vibrational excitation of SF6 scattering from graphite

We have observed vibrationally excited sulfur hexafluoride molecules in direct inelastic scattering from hot graphite surfaces. The vibrational temperature for the scattered flux has been determined by probing the effect of internal temperature on electron-induced fragmentation observed in mass spectra. The vibrational excitation depends on incident translational energy, E_tr, and a maximum temperature increase of 50 K is reached in direct scattering at E_tr = 2.5 eV. No effect of surface temperature has been observed at 950–1400 K. Inelastic angular distributions are reproduced by a collision complex model, and the experimental results are related to existing models for vibrational excitation.     

Rainbow scattering of CO and N2 from LiF(001)

The angular intensity distributions of CO and N(2) molecules scattered from a LiF(001) surface have been measured as functions of surface temperature, incident translational energy, and incident azimuthal direction affecting surface corrugation at a high resolution. Although both molecules have the same molecular mass and linear structure, only the CO molecule shows a rainbow feature in its scattering pattern, while the N(2) molecule shows a single peak distribution. From the comparisons of the obtained results with the calculated predictions based on the newly developed classical theory of the ellipsoid-washboard model, the differences in scattering distribution are attributed to the effects of molecular anisotropy and center-of-mass position. With an increase in the extent of the molecular anisotropy such as that of N(2) and CO as compared with rare-gas atoms, the summation of several scattering distributions depending on molecular orientation results in smearing the rainbow scattering on the corrugated surface. This smearing effect, however, attenuates when center-of-mass position deviates from the molecular center, as that for CO.     

Hyperthermal Ar atom scattering from a C(0001) surface

Experiments and simulations on the scattering of hyperthermal Ar from a C(0001) surface have been conducted. Measurements of the energy and angular distributions of the scattered Ar flux were made over a range of incident angles, incident energies (2.8-14.1 eV), and surface temperatures (150-700 K). In all cases, the scattering is concentrated in a narrow superspecular peak, with significant energy exchange with the surface. The simulations closely reproduce the experimental observations. Unlike recent experiments on hyperthermal Xe scattering from graphite [Watanabe et al., Eur. Phys. J. D 38, 103 (2006)], the angular dependence of the energy loss is not approximated by the hard cubes model. The simulations are used to investigate why parallel momentum conservation describes Xe scattering, but not Ar scattering, from the surface of graphite. These studies extend our knowledge of gas-surface collisional energy transfer in the hyperthermal regime, and also demonstrate the importance of performing realistic numerical simulations for modeling such encounters.     

Molecular Beam Studies on the Laser-Enhanced Surface Reaction of GaAs(100) with Chlorine

A cw supersonic Cl₂ molecular beam coupled with an angle-resolved time-of-flight (TOF) technique has been used to investigate the laser-enhanced surface reaction of GaAs(100) with chlorine. The mass and velocity distributions of the major reaction products under 1064 nm laser irradiation have been measured as a function of laser fluence, detection angle, surface temperature and normal component of the translational energy of the incident chlorine molecules. It has been found that increasing both laser fluence and the translational energy of incident chlorine molecules markedly enhance mis surface reaction. The measured flux angular distributions of major reaction products can be fit satisfactorily with a bi-cosine function. Measurements of the mass and angular distributions of reaction products by a modulated molecular beam mass spectrometry show that the surface temperature effect is obvious for the Cl₂/GaAs(100) “dark” thermal reaction. A direct activated dissociative chemisorption is proposed for the mechanism of Cl₂ chemisorption on the GaAs(100) surface.     

Angular intensity distribution of a molecular oxygen beam scattered from a graphite surface

The scattering of the oxygen molecule from a graphite surface has been studied using a molecular beam scattering technique. The angular intensity distributions of scattered oxygen molecules were measured at incident energies from 291 to 614 meV with surface temperatures from 150 to 500 K. Every observed distribution has a single peak at a larger final angle than the specular angle of 45° which indicates that the normal component of the translation energy of the oxygen molecule is lost by the collision with the graphite surface. The amount of the energy loss by the collision has been roughly estimated as about 30-41% based on the assumption of the tangential momentum conservation during the collision. The distributions have also been analyzed with two theoretical models, the hard cubes model and the smooth surface model. These results indicate that the scattering is dominated by a single collision event of the particle with a flat surface having a large effective mass. The derived effective mass of the graphite surface for the incoming oxygen is 9-12 times heavier than that of a single carbon atom, suggesting a large cooperative motion of the carbon atoms in the topmost graphene layer.     

A study of measured neutron elastic differential neutron cross sections for 23Na

Elastic neutron scattering angular distributions from ²³Na have been measured for incident neutron energies between 1.0 and 4.0 MeV at the University of Kentucky Accelerator Laboratory using neutron time-of-flight techniques for the scattered neutrons. This is an energy region in which existing data are very sparse. Measurements are compared with the predictions of the light particle-induced reaction code TALYS. The calculations reproduce forward angle scattering but have difficulty with relative minima in the differential cross section and large-angle scattering.     

On the determination of absolute vibrational excitation probabilities in molecule-surface scattering: Case study of NO on Au(111)

We describe a method to obtain absolute vibrational excitation probabilities of molecules scattering from a surface based on measurements of the rotational state, scattering angle, and temporal distributions of the scattered molecules and apply this method to the vibrational excitation of NO scattering from Au(111). We report the absolute excitation probabilities to the v = 1 and v = 2 vibrational states, rotational excitation distributions, and final scattering angle distributions for a wide range of incidence energies and surface temperatures. In addition to demonstrating the methodology for obtaining absolute scattering probabilities, these results provide an excellent benchmark for theoretical calculations of molecule-surface scattering.     

Electron energy loss spectroscopy of liquid glycerol

The inelastic scattering of low energy electrons from liquid glycerol has been studied. For the first time, electron energy loss spectra of liquids are sufficiently well resolved to permit the identification of vibrations corresponding to individual bonds, namely the C–H and O–H stretching vibrations in glycerol. The angular distribution of the specular peak is very broad, indicating the absence of long-range order at the surface of the liquid. The measurement of the loss signals as a function of the primary electron energy suggests a hybrid mechanism of excitation. The excitation mechanism for the O–H vibration has a stronger impact character as compared to the C–H vibration. A negative ion resonance of glycerol is found at a primary energy of 8 eV. The signal intensities measured as a function of the specular angle of the electron beam appear to be influenced by the angular dependence of the dipole and impact scattering cross-section and a possible preferred orientation of the C–H and O–H groups at the surface of the liquid.     

State dependence of rayleigh scattering from an=2 state of hydrogenlike atoms

We consider Rayleigh scattering from a hydrogenlike atom in an arbitrary excitedn=2 state, and we investigate theoretically the dependence of the scattered radiation intensity and Stokes parameters on the state multipoles for the case of unpolarized incident radiation. Because in then=2 case Rayleigh scattering can not be accompanied by the change of the electron angular momentum, only 10 out of the 16 state multipoles influence the scattered radiation attributes. Our study reveals the existence of a measurable quantity which is determined only by Rayleigh scattering from 2p states. For the particular case of excitation by electron impact, some quantitative predictions are made, at the photon scattering angle ?=π/2, based on values for the state multipoles extracted from the literature (Blum and Kleinpoppen, Band). The vicinity of Balmer α and Lyman α resonances are studied in detail.     

Quantum state-resolved CO2 collisions at the gas-liquid interface: surface temperature-dependent scattering dynamics

Energy transfer dynamics at the gas-liquid interface are investigated as a function of surface temperature both by experimental studies of CO2 + perfluorinated polyether (PFPE) and by molecular dynamics simulations of CO2 + fluorinated self-assembled monolayers (F-SAMs). Using a normal incident molecular beam, the experimental studies probe scattered CO2 internal-state and translational distributions with high resolution infrared spectroscopy. At low incident energies [Einc = 1.6(1) kcal/mol], CO2 J-state populations and transverse Doppler velocity distributions are characteristic of the surface temperature (Trot approximately Ttrans approximately TS) over the range from 232 to 323 K. In contrast, the rotational and translational distributions at high incident energies [Einc = 10.6(8) kcal/mol] show evidence for both trapping-desorption (TD) and impulsive scattering (IS) events. Specifically, the populations are surprisingly well-characterized by a sum of Boltzmann distributions where the two components include one (TD) that equilibrates with the surface (TTD approximately TS) and a second (IS) that is much hotter than the surface temperature (TIS > TS). Support for the superthermal, yet Boltzmann, nature of the IS channel is provided by molecular dynamics (MD) simulations of CO2 + F-SAMs [Einc = 10.6 kcal/mol], which reveal two-temperature distributions, sticking probabilities, and angular distributions in near quantitative agreement with the experimental PFPE results. Finally, experiments as a function of surface temperature reveal an increase in both sticking probability and rotational/translational temperature of the IS component. Such a trend is consistent with increased surface roughness at higher surface temperature, which increases the overall probability of trapping, yet preferentially leads to impulsive scattering of more highly internally excited CO2 from the surface.     

氯分子束与InP(100)表面反应散射的角分布研究

采用角分辨分子束散射技术研究了Cl_2与InP(100)表面热反应和激光诱导反应产物的角分布. 对于热反应, 由调制分子束和可转动四极质谱仪测得产物离子InCl~+、InCl_2~+、PCl~+、PCl_2~+和P_4~+的角分布, 都可用cos~(1.5)θ函数报合. 对于紫外(355 nm)激光诱导反应, 由飞行时间质谱法测得主要产物离子的角分布明显地偏离Knudsen定律. 其中In~+, InCl~+和InCl_2~+的角分布可用α·cosθ+(1-α)cos~nθ函数拟合, 其中α和n为拟合参数, 对于不同的产物离子有不同的数值. 由实验测得的脱附粒子的通量和能量在表面法线方向有明显地聚集现象, 可以认为产物从表面上脱附的机理, 除了热脱附之外, 还有非热脱附以及在表面附近脱附粒子的碰撞效应.     

In-plane polarisation correlation study of the 31 D state of helium excited by 40 eV electrons

Electron-photon polarisation correlations measured in the scattering plane defined by the incident and scattered electron momenta are reported for 40 eV electron impact excitation of the 3¹ D state of helium and for electron scattering angles in the range 40°≦?≦120°. When combined with the results of our earlier polarisation analysis on radiation emitted perpendicular to the scattering plane, detailed information on the shape and dynamics of the exicted state is obtained. In the small angular range of overlap (40–60°) there is excellent agreement with a pervious experimental study. The behaviour of the linear polarisation of the radiation emitted in the scattering plane is well reproduced by a multichannel eikonal theory for ?≦80°. Otherwise theories totally fail to described the excitation process.     

Rare gas collisions with molten metal surfaces

Newly available experimental data for the scattering of argon, neon, and xenon atoms from molten gallium, indium, and bismuth surfaces are compared to calculations with classical scattering theory. The results of the theory are in reasonable agreement with observed energy-resolved spectra taken at fixed angles, with in-plane angular distributions, and with the first available out-of-plane angular distribution spectra for these systems. For all three of the rare gases, scattering from liquid Ga required the use of an effective surface mass equal to 1.65 times the mass of a single Ga atom. The need for a larger effective mass has been noted previously for Ar/Ga scattering and is indicative of collective effects in the liquid Ga. Comparisons with data taken at low incident energies enable estimates of the physisorption well depth in the interaction potentials for many of the gas-metal combinations.     

Ab initio based tight-binding molecular dynamics simulation of the sticking and scattering of O2Pt(111)

The sticking and scattering of O(2)Pt(111) has been studied by tight-binding molecular dynamics simulations based on an ab initio potential energy surface. We focus, in particular, on the sticking probability as a function of the angle of incidence and the energy and angular distributions in scattering. Our simulations provide an explanation for the seemingly paradox experimental findings that adsorption experiments suggest that the O(2)Pt(111) interaction potential should be strongly corrugated while scattering experiments indicate a rather small corrugation. The potential energy surface is indeed strongly corrugated which leads to a pronounced dependence of the sticking probability on the angle of incidence. The scattered O(2) molecules, however, experience a rather flat surface due to the fact that they are predominantly scattered at the repulsive tail of the potential.     

Scattering of hyperthermal argon atoms from clean and D-covered Ru(0001) surfaces

Hyperthermal Ar atoms were scattered from a Ru(0001) surface held at temperatures of 180, 400 and 600 K, and from a Ru(0001)-(1×1)D surface held at 114 and 180 K. The resultant angular intensity and energy distributions are complex. The in-plane angular distributions have narrow (FWHM ≤ 10°) near-specular peaks and additional off-specular features. The energy distributions show an oscillatory behavior as a function of outgoing angle. In comparison, scattered Ar atoms from a Ag(111) surface exhibit a broad angular intensity distribution and an energy distribution that qualitatively tracks the binary collision model. The features observed for Ru, which are most evident when scattering from the clean surface at 180 K and from the Ru(0001)-(1×1)D surface, are consistent with rainbow scattering. The measured TOF profiles cannot be adequately described with a single shifted Maxwell-Boltzmann distribution. They can be fitted by two components that exhibit complex variations as a function of outgoing angle. This suggests at least two significantly different site and∕or trajectory dependent energy loss processes at the surface. The results are interpreted in terms of the stiffness of the surface and highlight the anomalous nature of the apparently simple hcp(0001) ruthenium surface.     

Surface induced ionization of neutral water clusters

The paper presents the results of study of a new phenomenon — the formation of cluster ions of both signs in the scattering of neutral water clusters by solid surfaces and the appearance of a current to the target. The experiments were carried out by the nozzle molecular beam technique. The probabilities of the charge removal from the surface were measured in dependence on incident angle, cluster size, and target material. The model of the process has been proposed which incorporates 1) formation of an ion pair during ion dissociation of a vibrationally excited molecule in a water cluster colliding with the surface; 2) asymmetric neutralization of an ion pair by surface; 3) inertial removal of a cluster ion from the surface. However the measured angular and energy distribution of emitted charged particles testify to more complex mechanisms of ionization and scattering because the spatial pattern of ion emission is of rainbow character and in some cases the direction of inertial removal (along the tangential component of initial velocity) does not dominate.     

Velocity map imaging of ion-molecule reactive scattering: the Ar(+)+ N(2) charge transfer reaction

We present a velocity map imaging spectrometer for the study of crossed-beam reactive collisions between ions and neutrals at (sub-)electronvolt collision energies. The charge transfer reaction of Ar(+) with N(2) is studied at 0.6, 0.8 and 2.5 eV relative collision energies. Energy and angular distributions are measured for the reaction product N. The differential cross section, as analyzed with a Monte Carlo reconstruction algorithm, shows significant large angle scattering for lower collision energies in qualitative agreement with previous experiments. Significant vibrational excitation of N(+)(2) is also observed. This theoretically still unexplained feature indicates the presence of a low energy scattering resonance.     

Scattering of light from oriented polymer films. II

A statistical theory for the scattering of light from oriented polymer films is developed in terms of angularly dependent generalized correlation functions. Numerical calculations of scattering patterns are carried out for special cases. The scattering depends upon two types of distributions describing (1) the orientation distribution of optical axes of scattering elements and (2) the angular dependence of correlation in orientation between pairs of optic axes. These distributions are expanded in Fourier series (in a two-dimensional treatment), the coefficients of which are functions of elongation and describe the elongation dependence of the scattering patterns.     

角分辨飞行时间法研究GaAs(100)表面蚀刻反应动力学

采用探测室可转动的分子束实验装置,研究了氯分子束与GaAs(100)表面热反应和紫外激光诱导反应的动力学.结果表明,热反应的主要产物为GaCl~3, 其角分布可用cos^2^.^3θ函数拟合.对于紫外(355nm)激光诱导反应,由角分辨的飞行时间(TOF)法测得主要产物为GaCl等,它们的通量角分布须用双余弦加和公式(c~1cosθ+c~2cos^nθ)拟合,表示产物粒子在表面法线方向明显聚集,而且由TOF 谱求得粒子的动能在表面法线方向最大. 这种明显的聚集现象可以由激光诱导的粒子在表面附近发生碰撞效应来解释