Energy dependence of the energy absorption buildup factor of HCO-materials

The energy absorption G-P fitting parameters and respective buildup factors for seven HCO-materials have been generated using the interpolation method in the energy range 0.015–15.0 MeV and up to a penetration depth of 40 mean free path. The generated buildup factor data has been studied as a function of incident photon energy and is presented in the form of graphs.     

Multiple valence electron detachment following Auger decay of inner-shell vacancies in gas-phase DNA

We have studied soft X-ray photoabsorption in the doubly deprotonated gas-phase oligonucleotide [dTGGGGT–2H]²⁻. The dominating decay mechanism of the X-ray induced inner shell vacancy was found to be Auger decay with detachment of at least three electrons, leading to charge reversal of the anionic precursor and the formation of positively charged photofragment ions. The same process is observed in heavy ion (12 MeV C⁴⁺) collisions with [dTGGGGT–2H]²⁻ where inner shell vacancies are generated as well, but with smaller probability. Auger decay of a single K-vacancy in DNA, followed by detachment of three or more low energy electrons instead of a single high energy electron has profound implications for DNA damage and damage modelling. The production of three low kinetic energy electrons with short mean free path instead of one high kinetic energy electron with long mean free path implies that electron-induced DNA damage will be much more localized around the initial K-shell vacancy. The fragmentation channels, triggered by triple electron detachment Auger decay are predominantly related to protonated guanine base loss and even loss of protonated guanine dimers is tentatively observed. The fragmentation is not a consequence of the initial K-shell vacancy but purely due to multiple detachment of valence electrons, as a very similar positive ion fragmentation pattern is observed in femtosecond laser-induced dissociation experiments.

A K-shell vacancy in DNA that is induced by a (therapeutically relevant) soft X-ray of MeV carbon ion, decays by Auger processes accompanied by emission of at least 3 low energy electrons.     

Large damage threshold and small electron escape depth in X-ray absorption spectroscopy of a conjugated polymer thin film

The information depth of near-edge X-ray absorption fine structure spectroscopy in the total electron yield mode (TEY-NEXAFS) is given by the escape depth of the TEY electrons z(TEY). This is determined by the effective ranges both of the inelastically scattered secondary electrons and of the primary excited electron before they thermalize below the vacuum level. For regioregular poly(3-hexylthiophene) (rreg-P3HT) thin films, we have measured the total electron emission efficiency to be 0.028 +/- 0.005 e/ph at an incident photon energy of 320 eV. The range of the primary electron was computed using optical dielectric-loss theory to be 7.5 nm. The range of the secondary electrons was then found by modeling to be 3.0 nm. This gives z(TEY) to be 2.5 nm, which is considerably less than the often-assumed value of 10 nm in the literature. It is also considerably smaller than the computed electron-electron scattering inelastic mean free path in the material, which suggests the predominance of electron-phonon scattering. Thus, TEY-NEXAFS has sufficient surface sensitivity to probe the frontier molecular layers of these organic conjugated polymers. In a second aspect of this report, the rreg-P3HT films have been characterized by in-situ core and valence photoemission spectroscopies and by ex-situ microattenuated total-reflection vibrational spectroscopy as a function of irradiation dose. No damage was observed in composition, bonding, orientation, and surface morphology under typical TEY-NEXAFS spectral acquisition conditions. For an integrated TEY that exceeds 2 x 10(-3) C cm(-2), however, the material degrades via alkyl side-chain dehydrogenation to unsaturated units, cross linking, ring opening of the backbone, and sulfur extrusion. Given that secondary electrons are the dominant cause of radiation damage, this exposure threshold measured by integrated TEY should also be valid at other X-ray energies.     

Quantification of hard X-ray photoelectron spectroscopy: Calculating relative sensitivity factors for 1.5- to 10-keV photons in any instrument geometry

A method for the rapid determination of theoretical relative sensitivity factors (RSFs) for hard X-ray photoelectron spectroscopy (HAXPES) instruments of any type and photon energy has been developed. We develop empirical functions to describe discrete theoretically calculated values for photoemission cross sections and asymmetry parameters across the photon energy range from 1.5 to 10 keV for all elements from lithium to californium. The formulae describing these parameters, in conjunction with similar practical estimates for inelastic mean free paths, allow the calculation of a full set of theoretical sensitivity factors for a given X-ray photon energy, X-ray polarisation and instrument geometry. We show that the anticipated errors on these RSFs are less than the typical errors generated by extracting X-ray photoelectron spectroscopy (XPS) intensities from the spectra and thus enable adequate quantification for any XPS/HAXPES experiment up to 10 keV. A spreadsheet implementation of this method is provided in the supporting information, along with example RSFs for existing commercial instruments.     

Influence of Thermal Radiation on Hot Cluster Decay Rates and Abundances

The influence of radiative cooling on the unimolecular decay rates of free, hot clusters and molecules with unspecified excitation energies is quantified. Two different regimes, dedined by the magnitude of the energy of the photons emitted, are identified and the boundary between them is given. The boundary is determined in terms of the photon emission rate constants and thermal properties of the particles. Also the abundance spectra are calculated for the continuous cooling case, corresponding to small photon energies. The two regimes correspond to continuous cooling and single photon quenching of the unimolecular decay. The radiative effect can be parametrized by a redefinition of the time each individual cluster has available to undergo evaporation, expressed by an effective radiative time constant.     

Yotta-photonic excitation spectroscopy of salicylidene-m-bromo-aniline

The observation of triplet-triplet absorption and emission spectra of salicylidene-m-bromo-aniline in solution, is complicated by the possible colored isomer formation during the optical pumping for yotta-photonic excitation at room temperature. The short-lived (singlet-singlet) and long-lived (triplet-triplet) absorption spectra were recorded phographically by microsecond flash and nano-second laser flash photolysis techniques. Salicylidene-m-bromo-aniline complexes were purified by repeated recrystallization until further recrystallization produced no further changes for X-ray diffraction pattern and optical absorption, emission properties. For yotta-photon excitation system, light could be faster than usual, because of heat and to many photonic collisions in the cavity, slowed down by the molecule, and stopped or frozen in a molecular orbital for a short time from nano-second to atto-second. The physical properties of the absorbed photons, in a very high photon flux density (i.e. in a photon field) are different in photonic character, and the emitted photons by the excited states behaves differently in photon field, no splitting occurs for the absorbed or emitted lines like in electrical or magnetic fields.     

Simple universal curve for the energy‐dependent electron attenuation length for all materials

An analysis is presented for a simple, universal equation for the computation of attenuation lengths (L) for any material, necessary for quantifying layer thicknesses in Auger electron spectroscopy (AES) and X‐ray photoelectron spectroscopy (XPS). Attenuation lengths for selected materials may be computed from the inelastic mean free path (λ_Opt) computed, in turn, from optical data. The computation of L involves the transport mean free path and gives good L values where values of λ_Opt are available. However, λ_Opt values are not available for all materials. Instead, λ may be calculated from the TPP‐2M relation, but this requires the accurate estimation of a number of materials parameters that vary over a wide range. Although these procedures are all soundly based, they are impractical in many analytical situations. L is therefore simply reexpressed, here, in terms of the average Z of the layer which may be deduced from the AES or XPS analysis, the average atomic size a (varies in a small range) and the kinetic energy E of the emitted electron. For strongly bonded materials, such as oxides and alkali halides, a small extra term is included for the heat of formation. A new equation, S3, is established with a root mean square (RMS) deviation of 8% compared with the values of attenuation length calculated from λ_Opt available for elements, inorganic compounds, and organic compounds. This excellent result is suitable for practical analysis. In many films, an average value of a of 0.25 nm is appropriate, and then L may be expressed only in terms of the average Z and E. Then, L expressed in monolayers, equation S4, exhibits an RMS deviation of 9% for many elements. These results are valid for the energy range 100 to 30 000 eV and for angles of emission up to 65°. Copyright © 2012 Crown copyright.     

Calculation of a divergence‐free lamb shift

A divergence‐free theory of the Lamb shift is presented, and calculations are carried out for hydrogen‐like ions. The theory uses two Lorentz‐invariant equations of motion, one for the electron in the presence of the photon, which is Dirac's four‐space time‐dependent equation, and the other for the photon in the presence of the electron. The electron–photon interaction is calculated from the Dirac current. The distribution of photon frequencies is bounded by the distribution of electron frequencies intrinsic to the Dirac current, thereby guaranteeing a divergence‐free result for the Lamb shift. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011     

Photon emission from massive projectile impacts on solids

First evidence of photon emission from individual impacts of massive gold projectiles on solids for a number of projectile-target combinations is reported. Photon emission from individual impacts of massive Au(n) (+q) (1 ≤ n ≤ 400; q = 1-4) projectiles with impact energies in the range of 28-136 keV occurs in less than 10 ns after the projectile impact. Experimental observations show an increase in the photon yield from individual impacts with the projectile size and velocity. Concurrently with the photon emission, electron emission from the impact area has been observed below the kinetic emission threshold and under unlikely conditions for potential electron emission. We interpret the puzzling electron emission and correlated luminescence observation as evidence of the electronic excitation resulting from the high-energy density deposited by massive cluster projectiles during the impact.     

A perspective on novel sources of ultrashort electron and X-ray pulses

Recently, much attention has been devoted to the development of new pulsed sources of radiation for investigating matter with atomic scale temporal and spatial resolution. While much has been achieved thanks to modern ultrafast laser technology, the ultimate coherent light source, the X-ray free electron laser (X-FEL), promises to deliver the highest X-ray photon flux in the shortest pulses at energies unreachable by conventional solid-state lasers. In parallel, other approaches that utilize electrons in table-top setups as a probe have been developed demonstrating the potential for a valid complement to X-ray based techniques. Here, we consider yet another possible avenue in which the technology of electron diffraction and imaging is pushed further; we estimate the interest and performances of a femtosecond high energy electron microscope and propose a hybrid experiment with relativistic electrons as a probe and fs X-ray pulses as a pump taking advantage of both technologies.     

Inhomogeneity of electron injection rates in dye-sensitized TiO2: comparison of the mesoporous film and single nanoparticle behavior

As it has been shown by pump-probe experiments electron injection at the interface between a dye molecule and mesoporous TiO2 proceeds with rates exceeding 1 x 10(13) s(-1). However, similar dye-TiO2 systems exhibit residual dye emission with lifetimes extending into the long nanosecond range. To address this inhomogeneity of injection rates time-correlated single photon counting microscopy was used to compare the emission behavior of dye-sensitized mesoporous films of TiO2 with that of individual anatase nanoparticles that had undergone extensive dialysis. The sensitized films produce intense residual emission with multiexponential decay components as long as 220 ns. The channels of mesoporous films contain physisorbed and trapped dye, which is the dominant source of the emission. It is likely that the wide range of lifetimes reflects the distribution of mean free paths experienced by the loose dye molecules diffusing within the film prior to undergoing oxidative quenching. In contrast, the intensity of emission from individual nanoparticles from which the loose dye was removed by dialysis is orders of magnitude lower. The lifetimes obtained from such particles are much shorter, with the primary component on a sub-nanosecond time scale. The presence of residual emission with a 230 ps lifetime shows that even on the surfaces of dialyzed nanoparticles there is a fraction of sensitizer molecules that do not inject electrons with the same high rate as is observed in ultrafast pump-probe experiments on films. Since the physisorbed dye was removed from these samples by dialysis, the residual emission is likely to originate from dye molecules bound to surface defects. Unusual collective emission bursts were observed in some of the measurements on sensitized nanoparticles. We attribute this behavior to stimulated emission from individual nanocrystallites.     

Synthesis and two‐photon absorption properties of conjugated polymers with N‐arylpyrrole as conjugated bridge and isolation moieties

Three novel conjugated polymers with N‐arylpyrrole as the conjugated bridge were designed and synthesized, which emitted strong one‐ or two‐photon excitation fluorescence in dilute tetrahydrofuran (THF) solution with high quantum yields. The maximal two‐photon absorption (TPA) cross‐sections of the polymers, measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in THF, were 752, 1114, and 1869 GM, respectively, indicating that the insertion of electron‐donating or electron‐withdrawing moieties into the polymer backbone could benefit to the increase of the TPA cross‐section. Their large TPA cross‐sections, coupled with the relatively high emission quantum yields, made these conjugated polymers attractive for practical applications, especially two‐photon excited fluorescence. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

SPECTRAL ANALYSES OF LOW LEVEL CHEMILUMINESCENCE OF A SHORT LIFETIME USING A HIGHLY SENSITIVE POLYCHROMATIC SPECTROMETER INCORPORATING A TWO DIMENSIONAL PHOTON-COUNTING TYPE DETECTOR

Abstract— Spectral analyses of low level chemiluminescence were carried out by using a newly developed polychromatic spectrometer in which a diffracted photon emission was detected simultaneously using a two dimensional photon-counting device. The spectrometer was sensitive in the 400–800 nm wavelength range. Low level chemiluminescence generated in a 1 nM luminol solution could be detected as a spectrum, showing a peak at 430 nm. Short lifetime photon emission from singlet oxygen showed only two peaks at around 630 and 700 nm in this highly time-resolved spectroscopy. Lipid peroxidation of linoleic acid by the lipoxygenase emitted a low intensity peak centered at 440 nm, but singlet oxygen emission arising from the decomposition of lipid peroxide was not observed. An injured cotyledon of a soybean seedling gave a broad emission centered at 725 nm in the absence of hydrogen peroxide, while in its presence a different emission peak appeared at a shorter wavelength (515 nm). Oxygenated, fluorescent components in the soybean seedling may be the emitting species. Singlet oxygen and triplet carbonyl groups were shown to be unlikely sources of the emission.     

Dependence of the recombination kinetics of geminate electron-ion pairs on the mean free path of electrons

We have investigated how the kinetics of geminate recombination of electron-ion pairs is influenced by the mean free path of electrons. By use of the Monte Carlo method previously developed the decay of the pair survival probability was numerically calculated for a variety of values of the mean free path of electrons. When the mean free path is negligibly small compared with the Onsager length, our result is in good agreement with the Hong-Noolandi result based on the Smoluchowski equation. However, as the mean free path increases, it deviates from their result increasingly. This indicates that the treatment based on the Smoluchowski equation is inadequate when the mean free path of electrons is not negligible compared with the Onsager length. We have found that for mean free paths comparable with or larger than the Onsager length the decay kinetics of the pair survival probability approximately follows the first-order kinetics except at very short and very long times. The dependence of the escape probability on the mean free path of electrons is also briefly discussed.     

Energy absorption buildup factors for thermoluminescent dosimetric materials and their tissue equivalence

Gamma ray energy-absorption buildup factors were computed using the five-parameter geometric progression (G-P) fitting formula for seven thermoluminescent dosimetric (TLD) materials in the energy range 0.015–15 MeV, and for penetration depths up to 40 mfp (mean free path). The generated energy-absorption buildup factor data have been studied as a function of penetration depth and incident photon energy. Buildup factors determined in the present work should be useful in radiation dosimetry, diagnostics and therapy. The tissue equivalence of TLD materials is also discussed.     

Radiative auger effect and extended X-ray emission fine structure (EXEFS).

Radiative Auger spectra are weak X-ray emission spectra near the characteristic X-ray lines. Radiative Auger process is an intrinsic energy-loss process in an atom when a characteristic X-ray photon is emitted, due to an atomic many-body effect. The energy loss spectra correspond to the unoccupied conduction band structure of materials. Therefore the radiative Auger effect is an alternative tool to the X-ray absorption spectroscopy such as EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure), and thus it is named EXEFS (Extended X-ray Emission Fine Structure). By the use of a commercially available X-ray fluorescence spectrometer or an electron probe microanalyzer (EPMA), which are frequently used in materials industries, we can obtain an EXEFS spectrum within 20 min. The radiative Auger effect, as an example, demonstrates that the study on atomic many-body effects has become a powerful tool for crystal and electronic structure characterizations. The EXEFS method has already been used in many industries in Japan. Reviews about the applications and basic study results on the radiative Auger effect are reported in this paper.     

Inelastic interactions of tunnel electrons with surfaces

Inelastic interactions of electrons emitted from the tip of a scanning tunnelling microscope (STM) are used to desorb individual hydrogen atoms from a Ge(111) surface. It is observed that the inelastic interactions depend not only on the electron energy and the current intensity but also on the electron emission regime of the STM tip. Quite surprisingly, it is found that tunnel electrons interact inelastically much less efficiently than field emitted electrons even though the electrons are in resonance with the Ge-H unoccuppied orbital.     

Metal/insulator/metal junctions for electrochemical surface science

We describe the preparation and characterization of Al-AlO_x-Ag tunnel junctions and calculate the energy distribution of the tunneling hot electrons in the range 0–2.5 eV above the Fermi level of silver. Because the mean free path of the hot electrons is of the order of the thickness of the silver film of the junction, which is at the same time the electrode in contact with an electrolyte, new surface effects can be studied. Hot electrons can be injected into the nonhydrated electron band in water. Hot electrons also cause hydrogen evolution at electrode potentials more positive than the ones needed in common electrochemistry. We observed the emission of hot electrons into silver during transients of hydrogen oxidation at silver and during oxidation of overpotential hydrogen on platinum clusters deposited on the silver electrode. The tunnel current at constant tunnel voltage can be changed by faradaic reactions, but surprisingly also by nonfaradaic reactions; this is assigned to a mesoscopic quantum phenomenon.     

Valence photoelectron spectroscopy of N2 and CO: recoil-induced rotational excitation, relative intensities, and atomic orbital composition of molecular orbitals

Recoil-induced rotational excitation accompanying photoionization has been measured for the X, A, and B states of N(2)(+) and CO(+) over a range of photon energies from 60 to 900 eV. The mean recoil excitation increases linearly with the kinetic energy of the photoelectron, with slopes ranging from 0.73×10(-5) to 1.40×10(-5). These slopes are generally (but not completely) in accord with a simple model that treats the electrons as if they were emitted from isolated atoms. This treatment takes into account the atom from which the electron is emitted, the molecular-frame angular distribution of the electron, and the dependence of the photoelectron cross section on photon energy, on atomic identity, and on the type of atomic orbital from which the electron is ejected. These measurements thus provide a tool for investigating the atomic orbital composition of the molecular orbitals. Additional insight into this composition is obtained from the relative intensities of the various photolines in the spectrum and their variation with photon energy. Although there are some discrepancies between the predictions of the model and the observations, many of these can be understood qualitatively from a comparison of atomic and molecular wavefunctions. A quantum-mechanical treatment of recoil-induced excitation predicts an oscillatory variation with photon energy of the excitation. However, the predicted oscillations are small compared with the uncertainties in the data, and, as a result, the currently available results cannot provide confirmation of the quantum-mechanical theory.     

Quantification of surface roughness effect on elastically backscattered electrons

Electron inelastic mean free path can be obtained from a measured elastic peak electron spectroscopy spectrum combined with a Monte Carlo simulation. It is thus necessary to know the influence of various experimental factors to the measured and calculated results. This work investigates the effect of the surface roughness or the surface topography on the intensity of the elastic peak. A Monte Carlo simulation, by taking into account of realistic surface roughness for both Gaussian and non‐Gaussian type rough surfaces experimentally prepared, has been employed to study the surface topography effect. The simulations of elastic peak electron spectroscopy were performed for both planar and rough Al and Cu surfaces and for varied primary energies ranging from 200 to 2000 eV. To quantify the surface roughness effect, the surface roughness parameter is introduced according to the ratio of elastic peak intensities between a rough surface and an ideal planar surface. Simulation results have shown that surface roughness parameter is important in a certain range of emission angle and particularly for large emission angles. For grazing emission, the elastic peak intensity can be largely enhanced by roughness even at nanometer scale. Copyright © 2014 John Wiley & Sons, Ltd.