Relativistic theory of tunnel and multiphoton ionization of atoms in a strong laser field

Relativistic generalization is developed for the semiclassical theory of tunnel and multiphoton ionization of atoms and ions in the field of an intense electromagnetic wave (Keldysh theory). The cases of linear, circular, and elliptic polarizations of radiation are considered. For arbitrary values of the adiabaticity parameter γ, the exponential factor in the ionization rate for a relativistic bound state is calculated. For low-frequency laser radiation , an asymptotically exact formula for the tunnel ionization rate for the atomic s level is obtained including the Coulomb, spin, and adiabatic corrections and the preexponential factor. The ionization rate for the ground level of a hydrogen-like atom (ion) with Z ? 100 is calculated as a function of the laser radiation intensity. The range of applicability is determined for nonrelativistic ionization theory. The imaginary time method is used in the calculations.     

Core binding energies for clusters deposited on different insulating substrates: esca spectra and theoretical electronic structure studies

The 4f core-level X-ray photoemission of small Pt clusters deposited on Teflon and SiO₂ substrates has been investigated. The experimental results are discussed and related to other data reported in the literature. Parallel results are presented for ab initio selfconsistent field, SCF, calculations of the core ionization potentials, IPs, of small Li clusters. These model calculations provide qualitative information about the nature and magnitude of the initial and final state contributions to the IPs for small clusters. We find that the binding energy shifts and linewidth broadening depend primarily on the cluster size and on the cluster substrate interaction. They do not result from electrostatic effects of the unit positive charge remaining on the ionized cluster. Our calculations show that this Coulomb effect does not apply to very small clusters.     

A new method for deriving atomic charges and dipoles for n, -alkanes: investigation of transferability and geometry dependence

Atomic charge models are known to be unsatisfactory for representing the ab initio electrostatic potential (ESP) of n, -alkanes. A new method for deriving atomic charges and dipoles is proposed and applied to n-alkanes ranging from C₄ to C₁₀. Electrostatic parameters found by this method reproduce accurately the ab initio ESP. The issues of transferability and conformational dependence are also addressed by introducing charges and dipoles taken from a truncated distributed multipole analysis, in the same spirit as the restrained electrostatic potential method. A transferable model is proposed for larger alkanes (>C₁₀). We also estimate the error made when using a set of Boltzmann-weighted electrostatic parameters for all conformers. The reduced number of electrostatic sites considered in our model makes it suitable for computer simulation of liquid n-alkanes.     

Electron impact ionization cross-section of C2, C3, Si2, Si3, SiC,SiC2 and Si2C

Total ionization cross-sections for C₂, C₃, Si₂, Si₃, SiC, SiC₂ and Si₂C molecules have been calculated by electron impact. Spherical complex optical potential formalism has been employed for obtaining the inelastic cross-sections for these molecules. Then by applying complex scattering potential-ionization contribution method, total ionization cross-sections are derived. These cross-sections are calculated in the energy range from ionization threshold to 2?keV. There are no measurements available in the literature to the best of our knowledge with which our results can be compared. The results show a linear relationship between maximum ionization cross-section and square root of the ratio of polarizability to ionization potential, depending on its atomicity. This gives a confirmation for the consistency of the data reported here. Present work is a maiden attempt to find electron impact ionization cross-section for these molecules, except for C₂ and C₃.     

On the relativistic generalization of Keldysh ionization theory

Relativistic generalization of the semiclassical theory of tunnel and multiphoton ionization of atoms and ions in the field of a high-intensity electromagnetic wave (Keldysh theory) with linear and elliptic polarizations is developed. The exponential factor in the ionization rate of relativistic bound state is calculated for arbitrary values of the adiabaticity parameter γ. In the case of low-frequency laser radiation, $\gamma \ll 1$, the asymptotically exact formula is derived for the ionization rate of atomic s-level, including the Coulomb, spin and adiabatic corrections and the pre-exponential factor. The ionization rate of the ground state of a hydrogen-like atoms (ions) with $Z\lesssim 100$ is calculated, depending on laser intensity and ellipticity of radiation.     

Scanning tunneling microscopy of fluorinated fullerene molecules on silicon surfaces

Scanning tunneling microscopy (STM) under ultra-high vacuum conditions is used to study the initial stages of adsorption of C₆₀F₁₈ and C₆₀F₃₆ fluorofullerene molecules on Si(111)-7 x 7 and Si(100)-2 x 1 surfaces. Spatially resolved STM images of individual molecules and ab initio calculations show that the fluorofullerene molecules interact with an Si surface, with the F atoms oriented toward the surface. The large electric dipole moment of the molecules induces strong polarization on the surface, but the charge transfer is weak. The presence of C₆₀F₃₆ isomers with different symmetry—T, C ₃, and C ₁—is revealed in STM images for the first time.     

Two-dimensional Penning ionization electron spectroscopic study on outer characteristics of molecules

Collision-energy/electron-energy-resolved two-dimensional Penning ionization electron spectroscopy (2D-PIES) has been used to study outer characteristics of molecules. Anisotropic potential energy surfaces for collisional ionization of molecules with a metastable helium atom He*(2³S) have been determined starting from ab initio model potentials via optimization based on trajectory calculations. Since ionization widths in the theoretical model of Penning ionization are functionals of target molecular orbitals, outer electron distributions of molecular orbitals can be determined via optimization procedures of calculated ionization cross-sections by trajectory calculations with respect to observed 2D-PIES data.     

The effect of inversion of the 1s ligand level splittings in gaseous inorganic salts

Using the results of calculations on the electronic structure of a number of molecules and model systems by ab initio and Discrete Variational Xα(DVM-Xα) methods, the inversion in the core level energy splitting of the ligand atoms on going from fluorine- to oxygen-containing inorganic salts in the gas phase is shown. The inversion is connected mainly with the fact that in oxygen-containing salts, such as LiNO₃, TiNO₃, LiClO₄ etc., the effect of pinning up the core levels of bridge oxygen atoms due to electronic density redistribution in the presence of the cation field prevails over the stabilizing influence of the cation electrostatic field. The qualitative notions presented may be used as a guide for the determination of the main geometrical configurations in gaseous inorganic salts and their associated compounds using the X-ray electronic spectroscopy method.     

Computational modeling of quantum-confined impact ionization in Si nanocrystals embedded in SiO2

Injected carriers from the contacts to delocalized bulk states of the oxide matrix via Fowler–Nordheim tunneling can give rise to quantum-confined impact ionization (QCII) of the nanocrystal (NC) valence electrons. This process is responsible for the creation of confined excitons in NCs, which is a key luminescence mechanism. For a realistic modeling of QCII in Si NCs, a number of tools are combined: ensemble Monte Carlo (EMC) charge transport, ab initio modeling for oxide matrix, pseudopotential NC electronic states together with the closed-form analytical expression for the Coulomb matrix element of the QCII. To characterize the transport properties of the embedding amorphous SiO₂, ab initio band structure and density of states of the α-quartz phase of SiO₂ are employed. The confined states of the Si NC are obtained by solving the atomistic pseudopotential Hamiltonian. With these ingredients, realistic modeling of the QCII process involving a SiO₂ bulk state hot carrier and the NC valence electrons is provided.     

强激光与高密度气体相互作用中电子和离子加速的数值模拟

在现有的一维粒子模拟程序的基础上发展了带光电离和碰撞电离及蒙特卡罗两体碰撞的模拟程序(1D PIC-MCC). 用此程序模拟研究了短脉冲激光与He气靶相互作用时电子和离子的加速过程. 研究表明当强激光与过临界密度的微米厚度的平面靶相互作用时，靶前表面物质将被激光脉冲前沿迅速离化；新生的电子被激光场有质动力加速成为高能电子，这些电子穿入到靶内，通过电子碰撞电离离化靶内物质；一部分高能电子穿透靶后，会在靶的后表面形成强的电荷分离场，该场迅速离化靶后表面物质，同时使得后表面离子得到加速. 部分穿透靶的超热电子将被电荷分离场重新拉回靶内，在靶的前后表面振荡. 一些振荡电子在此过程中得到电荷分离场加速，离开前表面，在前表面也形成电荷分离场，使前表面离子得到加速. 关键词： 激光等离子体 光电离和碰撞电离 电子加速 离子加速     

Dissociation of molecules in intense laser beam

Dissociation of molecules in the strong laser beam at the intensity of 10¹³–10¹⁴ W/cm² is investigated. Experimentally, the fragmentation of neutral molecules, CH₄, C₂H₄, C₄H₈; and the disintegration of molecular ions, CH ₄ ⁺ are studied by fluorescence spectroscopy and mass spectroscopy respectively. Some new phenomena, the strong dependence on the laser intensity, the universal dissociation, and the thorough fragmentation, are found in the fragmentation, and cannot be explained by the existing theories, as Coulomb Explosion theory or Re-scattering theory. We have suggested two new theories. The Super-excited State (SES) theory interprets the neutral fragmentation of molecules, which is stimulated to the SES by intense laser pulse. The Morse potential energy surface of the SES shows that either direct dissociation or pre-dissociation can take place in the SESs. Another theory, the theory of Field-assisted Dissociation (FAD) interprets the fragmentation of ionic molecules. According to this theory, the electric field of the laser pulse is involved directly to the dissociation process. QCT calculations for the trajectories moving on the dressed PES are performed. The result shows that the chemical bond which is parallel to the laser field vector undergo dissociation spontaneously. The dissociation takes place around 100 fs, which is in agreement with the ultrafast measurement in the pump-probe experiment.     

Multiphoton ionization of the hydrogen atom by a circularly polarized electromagnetic field

This paper examines the multiphoton ionization of the ground state of the hydrogen atom in the field of a circularly polarized intense electromagnetic wave. To describe the states of photoelectrons, quasiclassical wave functions are introduced that partially allow for the effect of an intense electromagnetic wave and that of the Coulomb potential. Expressions are derived for the angular and energy distributions of photoelectrons with energies much lower than the ionization potential of an unperturbed atom. It is found that, due to allowance for the Coulomb potential in the wave function of the final electron states, the transition probability near the ionization threshold tends to a finite value. In addition, the well-known selection rules for multiphoton transitions in a circularly polarized electromagnetic field are derived in a natural way. Finally, the results are compared with those obtained in the Keldysh-Faisal-Reiss approximation. Zh. éksp. Teor. Fiz. 116, 807–820 (September 1999)     

Tip-induced surface polarization: a new mechanism for contrast in the scanning tunnelling microscope

We propose a new mechanism influencing the contrast in STM images. It involves the polarization of the surface by the electric field from the tip; this affects the contrast when different parts of the surface have different polarizabilities. We demonstrate its importance for the case of ethene (C₂H₄) molecules adsorbed on the Si(001) surface; for this system we are able to obtain qualitative agreement between experiments and ab initio calculations by including the tip-induced field.     

Electron spectroscopy using excited atoms and photons IV. Penning ionization of ethylene

Using helium metastable atoms (2¹S, 2³S), the Penning ionization of C₂H₄ has been studied using a high resolution electrostatic electron analyzer. The Franck—Condon envelope for the ground state of C₂H₄⁺ (X²B_3u) is found to be the same for He* (2³S) Penning ionization and 584 Å photoionization. The ΔE shift values and the relative electronic transition probabilities are reported for four ionic states. Unusually large differences have been found for the relative electronic transition probabilities for Penning ionization and photoionization.     

Equilibrium composition and the effective adiabatic exponent of a clustering carbon plasma

The equilibrium composition and the effective adiabatic exponent of a low-temperature carbon plasma containing eight components (C, C₂, C₃, C₄, C₅, C⁺, C₂⁺, and e) are calculated. The temperature and pressure ranges are found in which polyatomic clusters form in a gas flow. It is shown that the effective adiabatic exponent of the carbon plasma is a nonmonotonic function of temperature. In the parameter range where the plasma consists largely of polyatomic clusters, the adiabatic exponent is close to unity. It is noted that anomalously low values of the effective adiabatic exponent indicate a considerable concentration of polyatomic molecules in the plasma jet. Such values can be observed in experiments with a low-temperature carbon plasma flowing about bodies.     

Synchrotron radiation VUV double photoionization of some small molecules

The VUV double photoionizations of small molecules (NO,CO,CO2 ,CS2 ,OSC and NH3 ) were investigated with photoionization mass spectroscopy using synchrotron radiation. The double ionization energies of molecules were determined with photoionization efficiency spectroscopy. The total energies of these molecules and their parent dications (NO2+ ,CO2+ ,CO2+2 ,CS2+2 ,OSC2+ and NH2+3 ) were calculated using the Gaussian 03 program and Gaussian 2 calculations. Then,the adiabatic double ionization energies of the molecules were predicated by using high accuracy energy mode. The experimental double ionization energies of these small molecules were all in reasonable agreement with their respective calculated adiabatic double ionization energies. The mechanisms of double photoionization of these molecules were discussed based on a comparison of our experimental results with those predicted theoretically. The equilibrium geometries and harmonic vibrational frequencies of molecules and their parent dications were calculated by using the MP2 (full) method. The differences in configurations between these molecules and their parent dications were also discussed on the basis of theoretical calculations.     

Coulomb explosion of nanoclusters that glide along organic surfaces

A model of the Coulomb multiple dissociation (Coulomb explosion) of a nanocluster that glides at an atomic distance along an organic film at a velocity that is lower than the Bohr velocity is proposed. Nanoclusters that consist of identical atoms and films, whose molecules contain substructures of periodic diatomic valence bonds, (for example, CnH_2n ) that have a significant dipole moment are considered. These structures can serve as antennas for IR radiation. It is shown that the dissociation process of a gliding nanocluster is induced by a picosecond pulse of highly intense photons (10¹⁴–10¹⁶ W/cm²) that are radiated by IR antennas of the film as a result of the relaxation of collective vibrating excitations that are accumulated in the antenna (excimoles). These excimoles resonantly exit from the IR antennas of the film as a result of the action of the periodic Coulomb field, which appears during the gliding of a nanocluster with respect to the film molecules at a rate below the Bohr velocity. In the framework of the proposed model, the experimental results on the decay of C ₆₀ ⁺ ions as they glide along an organic film that contains molecules with IR antennas are analyzed.     

Time-dependent perturbation calculations for transition properties of two-electron atoms under Debye plasma

Systematic investigation have been performed for the dynamic polarizabilities, energy levels, oscillator strengths and transition probabilities for the first few members of helium isoelectronic series He, Li⁺,Be²⁺,B³⁺ and C⁴⁺ embedded in the Debye plasma. The effect of plasma is described by introducing an exponential screening (the Debye screening) to the nuclear Coulomb potential. Systematic trend is observed for all the properties under study with respect to increased screening. The ionization potential decreases with an increased screening and the number of bound excited states supported by the Debye screened potential is finite.     

On the carbon suboxide bending potential (ν7)

An ab initio LCAO-MO-SCF calculation of the ν₇ bending potential of carbon suboxide (C₃O₂) is presented. The potential is found to have a double minimum with a barrier of 71.1 cm^?1, and minimum energy at a bending angle of 15.5°, in reasonable agreement with results obtained from spectroscopic measurements.     

Electron lucky-drift impact ionization coefficients of ZnS : Mn

Fit of the experimental data of ZnS : Mn by a modified lucky-drift formula has been performed using the least square algorithm. The fit agrees well with the experimental data only at high field. The best fitting parameters at high field are the mean free path of order 102.74 Å and Keldysh factor,p ₀ = 0.0138. A generalized Keldysh formula has been used, due to introduction of a soft threshold factor. The soft lucky-drift theory can also be used to calculate the impact ionization coefficients of high electron energy of ZnS : Mn without losing its physical significance compared to full band-structure Monte Carlo calculation with a remarkably reduced amount of computer resources. The curvature on semi-log plot of experimental impact ionization coefficient against the inverse of electric field is different from what is observed for other materials at low electric fields due to impact ionization of deep level impurities.