Core-electron binding energies in atoms and monolayers adsorbed on metallic substrates

A Born-Haber cycle analysis of photoemission from atoms and monolayers adsorbed on metallic surfaces elucidates the effects of the substrate on the initial and final state contributions to measured core-electron binding energies. For rare gases both a dependence on the work function of the substrate and on the final state screening energy are identified. Depending on the relative magnitudes of the work function of the substrate and the ionization potential of the core-ionized atom, the screening charge may reside either in the substrate or on the adsorbate atom itself. Within the monolayer range, the coverage-dependence of the core-electron binding energy is shown to be largely a final-state effect. The Born-Haber cycle relating the Auger decay energy of an adsorbed core-ionized atom to that of a similar free atom is also presented. These formulations are tested using data for Xe adsorbed on Pd and Cs.     

Electron-stimulated desorption of potassium and cesium atoms from oxidized molybdenum surfaces

The electron-stimulated desorption (ESD) yields and energy distributions for potassium (K) and cesium (Cs) atoms have been measured from K and Cs layers adsorbed at 300 K on oxidized molybdenum surfaces with various degrees of oxidation. The measurements were carried out using a time-of-flight method and surface ionization detector. The ESD appearance threshold for K and Cs atoms is independent of the molybdenum oxidation state and is close to the oxygen 2s level ionization energy of 25 eV. Additional thresholds for both K and Cs atoms are observed at about 40 and 70 eV in ESD from layers adsorbed on an oxygen monolayer-covered molybdenum surface; they are associated with resonance processes involving Mo 4p and 4s excitations. The ESD energy distributions for K and Cs atoms consist of single peaks. The most probable kinetic energy of atoms decreases in going from cesium to potassium and with increasing adsorbed metal concentration; it lies in the energy range around 0.35 eV. The K and Cs atom ESD energy distributions from adlayers on an oxygen monolayer-covered molybdenum surface are extended toward very low kinetic energies. The data can be interpreted by means of the Auger stimulated desorption model, in which neutralization of adsorbed alkali-metal ions occurs after filling of holes created by incident electrons in the O 2s, Mo 4s or Mo 4p levels.     

Resonances in the cesium atom yield in electron-stimulated desorption from tungsten coated with a germanium monolayer

The yield and energy distributions of Cs atoms emerging from cesium layers, which are adsorbed on tungsten coated with a thin germanium film (1-to 2-monolayers thick), have been measured as a function of the incident electron energy, the amount of adsorbed cesium, and the substrate temperature. The measurements were performed by the time-of-flight technique with a surface ionization detector. At low cesium coverages (Θ < 0.1), the Cs atom appearance threshold at a substrate temperature T = 160 K is ～24 eV, which correlates with the Cs 5s-level ionization energy. As the electron energy is increased, the yield passes through a broad plateau and reaches saturation. The signal intensity in the plateau region decreases gradually with increasing cesium coverage and tends to zero for Θ > 0.14. For Θ ≥ 0.15, the cesium atom appearance threshold shifts to ～30 eV, which corresponds to the Ge 3d-level ionization energy and the plateau is replaced by a resonance peak at ～38 eV, which can be identified with the ionization energy of the W 5p _3/2 level. This peak is observed only for Θ < 0.3 and T = 160 K. For Θ ≥ 0.3, there appears a resonance peak at ～50 eV, and for Θ ≥ 0.5, another resonance peak appears at ～80 eV. These peak positions correlate with the ionization energies of the W 5p _1/2 and W 5s levels, and their intensity is maximum at Θ = 1. The Cs atom energy distributions for Θ < 0.15 consist of a bell-shaped peak with a maximum at ～0.55 eV, and those for Θ ≥ 0.15 contain two nearly resolved maxima, a broad one peaking at ～0.5 eV and a narrow one at ～0.35 eV. The above results argue for the existence of three channels of Cs atom desorption. One channel involves reverse motion of the Cs²⁺ ion; another channel, neutralization of the adsorbed Cs⁺ ion following the Auger decay of a vacancy in the Ge atom; and the third channel involves desorption of a CsGe molecule as it is repelled from a W core exciton.     

用三色三光子电离光谱测量铀原子电离限附近能级

用三台可调谐脉冲染料激光器三步共振电离方法，测量铀原子在电离限附近的能级。测量了在４９７３３－５０２２４ｃｍ＾－１能量区的４０余个能级位置。     

Sm原子在电离限附近的光电离谱

用两脉冲激光两步激发和光电离的方法,观察了Sm原子在电离限附近的光电离谱,测定了在45321.8～45802.9cm~(-1)能量区间的70余个能级位置.     

H_2在Al_nCr(n=1-7)团簇上吸附和解离的密度泛函研究

采用密度泛函理论中的B3LYP方法研究了H2在AlnCr(n=1-7)团簇上的吸附和解离.结果表明:AlnCr团簇结构与Aln+1团簇结构相似;物理吸附是H2以侧向的形式吸附在Cr原子上,H-H键长略微增长,H2的振动频率发生了红移;除了n=5外,其它AlnCr H2团簇的最稳定结构均是AlnCr团簇的最稳定结构与两个氢原子成键而成;AlnCr团簇向H原子转移了电荷;AlnCr H2团簇的平均结合能,垂直电离势和能隙均大于AlnCr团簇的,即AlnCr H2团簇比AlnCr团簇更稳定;Al7Cr对H2的化学吸附表现出较强的惰性,而AlnCr H2(n=1,2,6)则表现出较强的化学活性;由化学反应路径跟踪可知,通过改变AlnCr团簇中Al原子的个数可以调节H2的物理化学吸附行为.     

H2在AlnCr(n=1-7)团簇上吸附和解离的密度泛函研究

采用用密度泛函理论中的B3LYP方法研究了H2在AlnCr(n=1-7)团簇上的吸附和解离。结果表明：AlnCr团簇结构与Aln+1团簇结构相似;物理吸附是H2是以侧向的形式吸附在Cr原子上,H-H键长略微增长,H2的振动频率发生了红移;除了n=5外,其它AlnCrH2团簇的最稳定结构均是AlnCr团簇的最稳定结构与两个氢原子成键而成;AlnCr团簇向H原子转移了电荷;AlnCrH2团簇的平均结合能,垂直电离势和能隙均大于AlnCr团簇的,即AlnCrH2团簇比AlnCr团簇更稳定;Al7Cr对H2的化学吸附表现出较强的惰性,而AlnCrH2(n=1,2,6)则表现出较强的化学活性;由化学反应路径跟踪可知,通过改变AlnCr团簇中Al原子的个数可以调节H2的物理化学吸附行为。     

CO在Ni(100)表面活化及硫中毒机理的ASED—MO研究

本文应用原子交迭和电子离域-分子轨道(ASED-MO)理论,研究了CO在Ni(100)表面活化及硫中毒机理。计算结果表明,CO顶位吸附比四度中心位吸附有更大的结合能。当CO分子被吸附于顶位时,其2π反键轨道将获得0.72个电子,解离能将从自由CO分子的11.1eV降到2.15eV。当吸附于四度中心位时,2π轨道将获得1.22个电子,解离能进一步降到1.85eV。由此看来,吸附于四度中心位的CO分子将具有更大的活性。当Ni(100)面上同时存在S原子吸附时,不同相对位置CO吸附结合能的计算结果表明,一个吸附S原子将“堵塞”四个最近邻顶位和四个最近邻中心位对CO的吸附作用,而对更远一些的吸附位则没有什么影响。这些结果支持了被吸附S原子对CO吸附的影响主要是近程性“结构效应”的观点。被吸附S原子的上述“堵塞”作用,吸附S原子后CO激活吸附位的减少,及可能存在的其它因素,构成了Ni表面的硫中毒。 关键词：     

Comparative analysis of the strong-field ionization of a quantum system with the Coulomb and short-range potentials

The dynamics of a hydrogen atom and a 3D model quantum system with a short-range potential is investigated using the direct numerical integration of the nonstationary Schrödinger equation in a wide range of laser intensities and frequencies. The simulation data are compared with the predictions of variants of the Keldysh-type theories. It is demonstrated that, in the low-frequency (tunnel) limit, the ionization rates of the systems with the Coulomb and short-range potentials and the same values of the ionization potential significantly differ from each other whereas, in the high-frequency (single-photon) limit, we do not observe a substantial difference between the ionization rates. Specific features of the angular distribution of the photoelectron emission and the photoelectron energy spectra are investigated in detail. In addition, the ionization suppression is studied for both Coulomb- and short-range-potential atoms. The stabilization is due to the dramatic reconstruction of the atom in the presence of a strong laser field and the formation of a new system (Kramers-Henneberger atom) that exhibits an increasing resistance to the ionization upon an increase in the laser intensity. In the two-photon ionization regime, the stabilization phenomenon is substantially more pronounced for the system with the Coulomb potential. This results from the effective excitation of the Rydberg states of the dressed atom in the strong-field limit.     

电场中Eu原子电离阈移动的实验研究

提出了一种新方法, 精确确定了稀土Eu原子第一电离阈的位置. 先用脉冲电场对Eu原子的高激发Rydberg态进行延时场电离探测, 再通过反向静电场排除光电离和自电离等其他路径所产生的离子信号的干扰, 观察并研究了Eu原子第一电离阈随着电场移动的规律. 由此所确定的零场下第一电离阈的数值与采用其他方法所确定的文献值^{[1, 2]}相一致, 从而验证了该方法的可靠性.     

Theory of hydrogen vibrations on transition metal surfaces

The site dependence of the vibration frequency, normal to the surface, of a neutrally adsorbed atom such as hydrogen on a transition metal surface is studied. The vibration frequency in the atop position is compared with the value in the metal-atom dimer. The bond length at the surface is found to be greater than in the dimer and to increase with increasing number of nearest neighbours. For strong bonding, the vibration frequency in the atop position is close to that in the dimer, and a comparison of the adsorbate vibration spectrum with that of molecular systems is justified. For weak binding the vibration frequencies are strongly shifted from the values of the dimer and such a comparison is not valid. In this limit the model of Froitzheim et al. is found to apply. A simple relation between the adsorption energy and vibration frequency is given. Bond relaxation is found to be very important in determining the vibration characteristics of adsorbed species.     

Electron stimulated desorption of cesium atoms from germanium-covered tungsten

The electron stimulated desorption (ESD) yield and energy distributions for Cs atoms from cesium layers adsorbed on germanium-covered tungsten have been measured for different Ge film thicknesses, 0.25-4.75 ML (monolayer), as a function of electron energy and cesium coverage Θ. The measurements have been carried out using a time-of-flight method and surface ionization detector. In the majority of measurements Cs is adsorbed at 300 K. The appearance threshold for Cs atoms is about 30 eV, which correlates well with the Ge 3d ionization energy. As the electron energy increases the Cs atom ESD yield passes through a wide maximum at an electron energy of about 120 eV. In the Ge film thickness range from 0.5 to 2 ML, resonant Cs atom yield peaks are observed at electron energies of 50 and 80 eV that can be associated with W 5p and W 5s level excitations. As the cesium coverage increases the Cs atom yield passes through a smooth maximum at 1 ML coverage. The Cs atom ESD energy distributions are bell-shaped; they shift toward higher energies with increasing cesium coverage for thin germanium films and shift toward lower energies with increasing cesium coverage for thick germanium films. The energy distributions for ESD of Cs from a 1 ML Ge film exhibit a strong temperature dependence; at T = 160 K they consist of two bell-shaped curves: a narrow peak with a maximum at a kinetic energy of 0.35 eV and a wider peak with a maximum at a kinetic energy of 0.5 eV. The former is associated with W level excitations and the latter with a Ge 3d level excitation. These results can be interpreted in terms of the Auger stimulated desorption model.     

Ionization of atoms in strong low-frequency electromagnetic field

The ionization of atoms in a low-frequency linearly polarized electromagnetic field (the photon energy is much lower than the ionization potential of an atom) is considered under new conditions, in which the Coulomb interaction of an electron with the atomic core in the final state of the continuum cannot be considered in perturbation theory in the interaction of the electron with the electromagnetic field. The field is assumed to be much weaker that the atomic field. In these conditions, the classical motion of the electron in the final state of the continuum becomes chaotic (so-called dynamic chaos). Using the well-known Chirikov method of averaging over chaotic variations of the phase of motion, the problem can be reduced to non-linear diffusion on the energy scale. We calculate the classical electron energy in the final state, which is averaged over fast chaotic oscillations and takes into account both the Coulomb field and the electromagnetic field. This energy is used to calculate the probability of ionization from the ground state of the atom to a lower-lying state in the continuum using the Landau-Dykhne approximation (to exponential accuracy). This ionization probability noticeably depends on the field frequency. Upon a decrease in frequency, a transition to the well-known tunnel ionization limit with a probability independent of the field frequency is considered.     

Electron-stimulated desorption of cesium atoms from cesium layers deposited on a germanium-coated tungsten surface

The yield and energy distribution of Cs atoms from cesium layers adsorbed on germanium-coated tungsten were measured, using the time-of-flight technique with a surface-ionization-based detector, as a function of the energy of bombarding electrons, germanium film thickness, the amount of adsorbed cesium, and substrate temperature. The threshold for the appearance of Cs atoms is ～30 eV, which correlates well with the germanium 3d-level ionization energy. As the electron energy increases, the Cs atom yield passes through a broad maximum at ～120 eV. For germanium film thicknesses from 0.5 to 2 monolayers, resonance Cs yield peaks were observed at electron energies of 50 and 80 eV, which can be related to the tungsten 5p and 5s core-level ionization energies. As the cesium coverage increases, the Cs atom yield passes through a flat maximum at monolayer coverage. The energy distribution of Cs atoms follows a bell-shaped curve. With increasing cesium coverage, this curve shifts to higher energies for thin germanium films and to lower energies for thick films. The Cs energy distribution measured at a substrate temperature T = 160 K exhibits two bell-shaped peaks, namely, a narrow peak with a maximum at ～0.35 eV, associated with tungsten core-level excitation, and a broad peak with a maximum at ～0.5 eV, deriving from the excitation of the germanium 3d core level. The results obtained can be described within a model of Auger-stimulated desorption.     

Semiempirical model calculations for chemisorption on transition metals: III. CO,N2 and NO on Ni,Cu, Pd and Ag

An effective one electron Hamiltonian is used to calculate the qualitative behaviour of various physical quantities (adsorption energy, shifts of ionization energies, energy profiles, etc.) over a series of different adsorption systems. The numerical calculations allow for several orbitals on the adsorbed particle as well as for the s- and the d-and in the metal. The experimentally found trends concerning the general features of photoelectron spectra and the variation of the adsorption energy with adsorbate and substrate as well as with the surface orientation and the location of the adsorbed species are reproduced reasonably well. A simple theory of photoemission (the final state is a plane wave) has been combined with the semiempirical calculations. The generally observed decrease of emission from the d-band region can be understood as an interference effect in the initial state.     

Inelastic electron collisions with Rydberg atoms

The standard classical method of computer simulation is used for evaluation of the inelastic cross section in electron collisions with a highly excited (Rydberg) atom. In the course of collision, the incident and bound electrons move along classical trajectories in the Coulomb field of the nucleus, and the scattering parameters are averaged over many initial conditions. The reduced ionization cross section of a Rydberg atom by electron impact approximately corresponds to that of atoms in the ground states with valence s-electrons and coincides with the results of the previous Monte Carlo calculations. The cross section of an atom transition between Rydberg atom states as a result of electron impact is used for finding the stepwise ionization rate constant of atoms in collisions with electrons or the rate constant of three-body electron-ion recombination in a dense ionized gas because these processes are determined by kinetics of highly excited atom states. Surprisingly, the low-temperature limit of electron temperatures is realized when the electron thermal energy is lower than the atom ionization potential by about three orders of magnitude, as follows from the kinetics of excited atom states. The article is published in the original.     

Electron-stimulated desorption of lithium atoms from oxidized molybdenum surface

The yield and energy distributions of lithium atoms upon electron-stimulated desorption from lithium layers adsorbed on the molybdenum surface coated with an oxygen monolayer have been measured as functions of the impact electron energy and lithium coverage. The measurements are performed using the time-of-flight technique and a surface ionization detector. The threshold of the electron-stimulated desorption of lithium atoms is equal to 25 eV, which is close to the ionization energy of the O 2s level. Above a threshold of 25 eV, the yield of lithium atoms linearly increases with an increase in the lithium coverage. In the coverage range from 0 to 0.45, an additional threshold is observed at an energy of 55 eV. This threshold can be associated with the ionization energy of the Li 1s level. At the electron energies above a threshold of 55 eV, as the coverage increases, the yield of lithium atoms passes through a maximum at a coverage of about 0.1. Additional thresholds for the electron-stimulated desorption of the lithium atoms are observed at electron energies of 40 and 70 eV for the coverages larger than 0.6 and 0.75, respectively. These thresholds correlate with the ionization energies of the Mo 4s and Mo 4p levels. Relatively broad peaks in the range of these thresholds indicate the resonance excitation of the bond and can be explained by the excitation of electrons toward the band of free states above the Fermi level. The mean kinetic energy of the lithium atoms is equal to several tenths of an electronvolt. At electron energies less than 55 eV, the energy distributions of lithium atoms involve one peak with a maximum at about 0.18 eV. For the lithium coverages less than 0.45 and electron energies higher than 55 eV, the second peak with a maximum at 0.25 eV appears in the energy distributions of the lithium atoms. The results obtained can be interpreted in the framework of the Auger-stimulated desorption model, in which the adsorbed lithium ions are neutralized after filling holes inside inner shells of the substrate and lithium atoms.     

Molecular orbital study of co chemisorption and oxidation on a Pt(111) surface

A molecular orbital study was made, using an atom superposition and electron delocalization (ASED) technique, of the structures and energy levels of CO on Pt(111) surface. CO is predicted to be preferentially adsorbed at a height of 2.05 Å from the surface at a 1-fold position with the carbon end down. The calculated binding energy (1.7 eV) is in good agreement with the recent experimental result (1.5 eV) of Campbell et al. Calculated binding energies for bridging (1.3 eV) and high coordinate (1.1 eV) sites are predicted to be smaller in magnitude. Calculated results are used to discuss the ordering of energy levels of adsorbed CO. The interaction between CO (adsorbed) and O (adsorbed) has been studied to estimate the energy of activation for the oxidation of CO on Pt(111) surface. The calculated activation energy (1.6 eV) is in reasonable agreement with the recent experimental result (1 eV) of Campbell et al. The Langmuir-Hinshelwood mechanism is found to be favored. We predict CO₂ bonds vertically.     

Long range and temperature-dependent interaction between an alkali atom and a metallic surface; application to surface ionization

For explaining some long range and temperature dependent charge transfer involved in surface processes dealing with particles leaving a surface, we extend the usual chemisorption theory to larger distances. Treating the interaction of an alkali atom (lithium and sodium) on a metal surface (rhenium) in the chemisorption model, we introduce the temperature in the expression for the effective charges of the adsorbed atom. These effective charges are shown to be very sensitive to the temperature for atom-surface distances larger than 5 Bohr radii. The Coulomb repulsion effect between opposite spin electrons on the adsorbed particle allows us to describe the effective charges of both the positive and negative adsorbed ions. We apply our treatment to the positive surface ionization of thermal particles and give a new expression of the degree of ionization which asymptotically tends to the values of the Saha-Langmuir law. We found that the surface ionization process occurs at distances slightly decreasing with increasing temperatures, which are of the order of 13 Bohr radii for lithium on rhenium and of 15 Bohr radii for sodium on rhenium.     

Testing neutrino magnetic moment in ionization of atoms by neutrino impact

The atomic ionization processes induced by scattering of neutrinos play key roles in the experimental searches for a neutrino magnetic moment. Current experiments with reactor (anti)neutrinos employ germanium detectors having energy threshold comparable to typical binding energies of atomic electrons, which fact must be taken into account in the interpretation of the data. Our theoretical analysis shows that the so-called stepping approximation to the neutrino-impact ionization is well applicable for the lowest bound Coulomb states, and it becomes exact in the semiclassical limit. Numerical evidence is presented using the Thomas-Fermi model for the germanium atom.