Chemisorption of pyridine and pyrrole on iron oxide surfaces studied by XPS

Adsorption of pyridine and pyrrole on model iron oxide surfaces has been studied by X-ray photoelectron spectroscopy. At room temperature both molecules adsorb with their molecular identity intact. Upon heating above 320 K pyridine decomposes on the surface whereas pyrrole desorbs intact at 345 K. The bonding of pyridine and pyrrole to the surface at room temperature is studied by monitoring the change in measured N(1s) and C(1s) binding energies between gas-phase molecules and the monolayer phase at room temperature. The results suggest that pyridine bonds via electron donation from the non-bonding nitrogen lone pair to the surface while pyrrole bonds via electron donation from a π-bonding orbital to the surface. The differences in surface bonding are interpreted in the context of the concept of Lewis acids and bases applied to surfaces.     

Simultaneous energy and timing decisions in time differential perturbed angular correlation experiments using BaF2 scintillators

BaF₂ scintillation counters, coupled to constant fraction differential discriminatiors, permit simultaneous energy and timing decisions in recording delayed coincidence spectra. We explore the advantages and limitations of this innovation in time differential perturbed angular correlation experiments, and illustrate it for¹¹¹CdNi and¹⁰⁰RhNi.     

Coulombic energy transfer and triple ionization in clusters

Using neon and its dimer as a specific example, it is shown that excited Auger decay channels that are electronically stable in the isolated monomer can relax in a cluster by electron emission. The decay mechanism, leading to the formation of a tricationic cluster, is based on an efficient energy-transfer process from the excited, dicationic monomer to a neighbor. The decay is ultrafast and expected to be relevant to numerous physical phenomena involving core holes in clusters and other forms of spatially extended atomic and molecular matter.     

Ab initio calculation of correlation effects for the O 1s core electron binding energy in MgO

Wavefunction based ab initio embedded cluster calculations are employed to calculate the O 1s core electron binding energies (CEBEs) of bulk MgO and the MgO(001) surface. A quantum cluster consisting of 61 atoms in five layers and embedded in a large point charge field is used for bulk MgO, the cluster for the MgO(001) surface is chosen accordingly. The O 1s CEBEs are calculated at the Koopmans' theorem (KT) and ΔSCF levels and with inclusion of correlation effects by means of the MC-CEPA method (multi-configuration coupled electron pair approximation), which is an approximate multi-reference coupled cluster approach. The correlation contributions to the O 1s CEBE of the central O atom due to the Mg atoms in the first and the O atoms in the second coordination shell turned out to be additive to a large extent. Therefore, they could be evaluated in an incremental fashion by a series of smaller calculations, where only a few atoms are included in the correlation treatment rather than all atoms of the first coordination shells or of the full quantum cluster. This makes the calculations feasible, even if large basis sets are used. The final results for the O 1s CEBEs are 533.47 and 533.50 eV for bulk MgO and the MgO(001) surface, to which electron correlation contributes 0.77 and 0.70 eV, respectively.     

Tunneling ionization of atoms with excitation of the core

A general formula is obtained for the probability of tunneling ionization of an atom accompanied by excitation of the core. This formula is a generalization of the Carlson formula for the probability of a single-photon two-electron transition in atoms. The limiting case of this formula, just as that of the Carlson formula, is the well-known random-perturbations approximation. Numerical results are presented for Zn, Sr, and Cd atoms. For these atoms the contribution of the excited states of singly charged ions to the probability of the formation of doubly charged ions is a nonmonotonic function of the laser radiation intensity. Analysis of the tunneling ionization of molecules shows that with overwhelming probability an ion is formed in the ground vibrational state, while for the standard photoionization the distribution over vibrational states is determined by the Franck-Condon factors.     

Relaxation effects during core ionization in metal—metal-bonded complexes

Using the ligand group shift model to calculate metal binding energies (BE's), comparisons of BE(calc) and BE(obs) values reveal a correlation between relaxation energy and the extent of metal—metal bonding. No significant difference in relaxation energy is detected between monometal complexes and the dipalladium complexes which contain a single MM bond. However, substantially larger relaxation energies (1–2 eV) relative to monometal complexes are found for multiply MM-bonded complexes. The magnitude of the additional relaxation energy is in the range expected on the basis of comparisons with other systems.     

Many-body Hamiltonian with screening parameter and ionization energy

We prove the existence of a Hamiltonian with ionization energy as part of the eigenvalue, which can be used to study strongly correlated matter. This eigenvalue consists of total energy at zero temperature (E ₀) and the ionization energy (ξ). We show that the existence of this total energy eigenvalue, E ₀±ξ, does not violate the Coulombian atomic system. Since there is no equivalent known Hamilton operator that corresponds quantitatively to ξ, we employ the screened Coulomb potential operator (Yukawa-type), which is a function of this ionization energy to analytically calculate the screening parameter (σ) of a neutral helium atom in the ground state. In addition, we also show that the energy level splitting due to spin-orbit coupling is inversely proportional to ξ eigenvalue, which is also important in the field of spintronics.     

Electron correlation in fast ion-impact single ionization of helium atoms

A four-body distorted-wave approximation is applied for theoretical analysis of the fully differential cross sections(FDCS)for proton-impact single ionization of helium atoms in their ground states.The nine-dimensional integrals for the partial amplitudes are analytically reduced to closed-form expressions or some one-dimensional integrals which can be easily calculated numerically.Calculations are performed in the scattering and perpendicular planes.The influence of the target static electron correlations on the process is investigated using a number of different bound-state wave functions for the ground state of the helium targets.An illustrative computation is performed for 75-ke V proton–helium collisions and the obtained results are compared with experimental data and other theoretical predictions.Although for small momentum transfers,the comparison shows a reasonable agreement with experiments in the scattering and perpendicular planes,some significant discrepancies are still present at large momentum transfers in these planes.However,our results are compatible and for some cases,better than those of the other sophisticated calculations.     

Effect of the corrected ionization potential and spatial distribution on the angular and energy distribution in tunnel ionization

Within the framework of the Ammosov–Delone–Krainov theory, we consider the angular and energy distribution of outgoing electrons due to ionization by a circularly polarized electromagnetic field. A correction of the ground ionization potential by the ponderomotive and Stark shift is incorporated in both distributions. Spatial dependence is analyzed.     

Accurate core ionization potentials and photoelectron kinetic energies for light elements

By electron spectroscopy we have determined accurate values for the neon 1s ionization potential (870.312±.017 eV) and the neon Auger (¹D₂) k     

Role of elastic scattering in high-order above threshold ionization

We investigate the target and intensity dependence of plateau in high-order above threshold ionization(HATI) by simulating the two-dimensional(2D) momentum distributions and the energy spectra of photoelectrons in HATI of rare gas atoms through using the quantitative rescattering model. The simulated results are compared with the existing experimental measurements. It is found that the slope of the plateau in the HATI photoelectron energy spectrum highly depends on the structure of elastic scattering differential cross section(DCS) of laser-induced returning electron with its parent ion. The investigations of the long- and short-range potential effects in the DCSs reveal that the short-range potential, which reflects the structure of the target, plays an essential role in generating the HATI photoelectron spectra.     

Triple differential cross section in ionization of hydrogen by electron impact

A novel model is proposed to study the ionization of atomic hydrogen by fast election impact in coplanar asymmetric geometry making use of the post form of the transition matrix element for the energy shell and the two-potential formula. Based on the approximation of projectile plane waves and three-body problems, the transition matrix element is decomposed into two parts: the structure and scattering factor and the correlation factor. The contributions of these factors to triple differential cross sections are investigated using the method of asymptotic and convergent series.     

Threshold energy for impact ionization by holes in GaAs

Various processes have been considered for impact ionization by holes in GaAs and the corresponding threshold energies have been reported.     

Laser-assisted particle-atom ionization. Analysis of triple and double differential cross-sections

Summary Based on a theoretical model worked out previously, an analysis is reported of triplet and double differential cross-section of hydrogen atom ionization by electron impact in the presence of a single-mode, homogeneous, linearly polarized, off-resonance laser field. In particular, calculations are carried out to investigatea) the dependence of the cross-sections on the field strength,b) the average number of exchanged photons,c) the limits of validity of a known sum rule. The reported results improve considerably the present knowledge of this kind of elementary stimulated atomic process. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Bound on the ionization energy of large atoms

We present a simple argument which gives a bound on the ionization energy of large atoms that implies the bound on the excess charge of Fefferman and Seco [2].Supported by a Sloan Dissertation Fellowship. Address from September 1989: Department of Mathematics, Caltech, Pasadena, CA 91125, USASupported in part by NSERC Grant N. A7901Supported by a Danish Research Academy Fellowship and U.S. National Science Foundation Grant PHY-85-15288-A03. Address from September 1989: Department of Mathematics, University of Michigan, Ann Arbor, MI 48109, USA     

Electron energy distribution function in ionization waves of different amplitudes

The changes of the body and of the tail of the electron energy distribution function are studied in dependence on amplitudes of ionization waves in neon.