Photoionization Cross Sections Research Articles

Photoionization of nS and nD Rydberg atoms of Rb and Cs from the near-infrared to the ultraviolet spectral region

We present calculations of the photoionization (PI) cross sections of rubidium and cesium Rydberg atoms for light with wavelengths ranging from the infrared to the ultraviolet, using model potentials from Marinescu et al (1994 Phys. Rev. A 49 982). The origins of pronounced PI minima are identified by investigating the free-electron wavefunctions. These include broad PI minima in the nS to ϵP PI channels of both Rb and Cs, with free-electron energy ϵ, which are identified as Cooper minima. Much narrower PI minima in the nD to ϵF channels are due to shape resonances of the free-electron states. We describe possible experimental procedures for measuring the PI minima, and we discuss their implications in fundamental atomic physics as well as in practical applications. Measurements of PI cross sections of Rydberg atoms may serve as a sensitive probe for many-electron interactions of the Rydberg electron in the atomic core region.

Photoionization of Rydberg atoms in optical lattices

We develop a formalism for photoionization (PI) and potential energy curves (PECs) of Rydberg atoms in ponderomotive optical lattices and apply it to examples covering several regimes of the optical-lattice depth. The effect of lattice-induced PI on Rydberg-atom lifetime ranges from noticeable to highly dominant when compared with natural decay. The PI behavior is governed by the generally rapid decrease of the PI cross sections as a function of angular-momentum (ℓ), lattice-induced ℓ-mixing across the optical-lattice PECs, and interference of PI transition amplitudes from the lattice-mixed into free-electron states. In GHz-deep lattices, ℓ-mixing leads to a rich PEC structure, and the significant low-ℓ PI cross sections are distributed over many lattice-mixed Rydberg states. In lattices less than several tens-of-MHz deep, atoms on low-ℓ PECs are essentially ℓ-mixing-free and maintain large PI rates, while atoms on high-ℓ PECs trend towards being PI-free. Characterization of PI in GHz-deep Rydberg-atom lattices may be beneficial for optical control and quantum-state manipulation of Rydberg atoms, while data on PI in shallower lattices are potentially useful in high-precision spectroscopy and quantum-computing applications of lattice-confined Rydberg atoms.

Photoionization cross-section in a GaAs spherical quantum shell: the effect of parabolic confining electric potentials

Photoionization cross-section in a GaAs spherical quantum shell: the effect of parabolic confining electric potentials

Photoionization cross sections of the ground and first excited states of the OH radical

We present a comprehensive study of photoionization of OH radicals from the ground and first excited electronic states. Cross sections and asymmetry parameters for the valence orbitals are reported for photon energies from near the threshold to 60 eV. The calculations have been performed with the $R$-matrix method. Two different continuum basis types, namely, the Gaussian and $B$-spline bases, are used to assess the quality of the description of the continuum. The results show both types of continuum bases provide a similar quality description in the near threshold resonant region, but the latter can predict more reliable photoionization observables in higher-energy regions. Our calculations are compared with available experimental and theoretical results, and the discussions are provided.

Lyman and Balmer Continuum Spectra for Hydrogen Atoms in Strong White Dwarf Magnetic Fields

Abstract We report calculations of photoionization cross sections for hydrogen atoms in white-dwarf magnetic fields. The calculations were implemented using the adiabatic-basis-expansion method and the coupled-channel theory, which are valid for low and high magnetic fields, respectively. The magnetic fields span over a typical white-dwarf strength regime from 23.5 to 2350 MG. Lyman and Balmer continuum spectra for bound–free transitions in magnetic white-dwarf stars are presented with various field strengths. The current results are compared with those from the complex-rotation method. Excellent agreement is shown in the energy region away from Landau thresholds, but the pronounced discrepancies are found in the small vicinity below Landau thresholds. The agreement shown illustrates the reliability of these two theoretical approaches used, while the discrepancies should be attributed to the limitation of the complex-rotation method. The photoionization cross sections presented here should be applicable to the analyses of continuum spectra and their polarization properties observed in the atmospheres of hydrogen-dominated magnetic white dwarfs.

Observation of low‐temperature chemistry products in laminar premixed low‐pressure flames by molecular‐beam mass spectrometry

AbstractThe formation of typical low‐temperature oxidation products is observed in laminar premixed low‐pressure flames investigated by photoionization molecular‐beam mass spectrometry at the Swiss Light Source. The C1–C4 alkyl hydroperoxides can be identified in n‐butane‐ and 2‐butene‐doped hydrogen flames by their photoionization efficiency spectra at m/z 48, 62, 76, and 90. C1–C3 alkyl hydroperoxides are also observed in a propane‐doped hydrogen flame and in a neat propane flame. In addition, threshold photoelectron spectra reveal the presence of the alkyl hydroperoxides. In the 2‐butene/H2 flame, the photoionization spectrum at m/z 88 also enables the identification of butenyl hydroperoxides by comparison with calculated ionization energies of the alkenyl hydroperoxides and a literature spectrum. The low‐temperature species are formed close to the burner surface with maximum mole fractions at 0.25–0.75 mm above the burner. At 0.5 mm, even the methylperoxy radical (CH3OO) is measured for the first time in a laminar premixed flame. The rate of production analyses show that consumption of the hydroperoxyalkyl radicals results in the formation of cyclic ethers. In the n‐butane/H2 flame, ethylene oxide, oxetane, and methyloxirane are identified. Besides expected small oxygenated species, for example, formaldehyde or acetaldehyde, the larger C4 oxygenates butanone (C2H5COCH3) and 2,3‐butanedione (C4H6O2) are formed in the two C4 hydrocarbon‐doped hydrogen flames. Quantification of alkyl hydroperoxides with estimated photoionization cross sections based on the corresponding alcohols, which have similar photoelectron structures to the alkyl hydroperoxides, shows that mole fractions are on the order of 10−5–10−6 in the n‐butane/H2 flame. Measurements are corroborated by simulations, which also predict the presence of some peroxides in detectable concentrations, that is, mole fractions larger than 10−7, under the investigated conditions. The observation of peroxide species and cyclic ethers in the investigated laminar premixed flames give new insights into the contribution of low‐temperature combustion chemistry in a flame.

Direct observation of spin-resolved valence band electronic states from a buried magnetic layer with hard X-ray photoemission

ABSTRACT We report spin-resolved hard X-ray photoelectron spectroscopy (spin-HAXPES) for a buried Fe thin film in the valence band region. For the spin-HAXPES experiments, we developed an ultracompact built-in Mott-type spin-filter in a sample carrier, which enabled us to use the merit of two-dimensional (2D) multi-channel detector in a recent photoelectron analyser without modifying an apparatus for HAXPES. The effective Sherman function and the single-channel figure of merit (FOM) of the spin-filter were assessed to be −0.07 and 2.0 × 10−4, respectively. By utilizing the 2D detector of the photoelectron analyser, the effective FOM increased by a factor of ~4 × 104 compared to the case when only 1 channel of the 2D detector was used. We have applied spin-HAXPES to MgO(2 nm)/Fe(50 nm)/MgO(001) structures. The spin-HAXPES experiments revealed the majority and minority spin electronic states and the spin polarisation of the buried Fe thin film. Due to the large photoionization cross-section of the 4s orbital of Fe in HAXPES, the spin-resolved spectra mainly reflected the Fe 3d and 4s states. The observed spin-HAXPES and spin polarisation spectral shapes agreed well with the calculated spin-resolved cross-section weighted densities of states and spin polarisation spectra. In contrast, a small discrepancy in the energy scale was recognised due to the electron correlation effects. These results suggest that the electron correlation effects are important in the electronic structure of bulk Fe, and spin-HAXPES is useful for detecting genuine spin-resolved valence band electronic structures of buried magnetic materials.

Photoionization Cross-Sections of Carbon-Like N+ Near the K-Edge (390–440 eV)

High-resolution K-shell photoionization cross-sections for the C-like atomic nitrogen ion (N+) are reported in the 398 eV (31.15 Å) to 450 eV (27.55 Å) energy (wavelength) range. The results were obtained from absolute ion-yield measurements using the SOLEIL synchrotron radiation facility for spectral bandpasses of 65 meV or 250 meV. In the photon energy region 398–403 eV, 1s⟶2p autoionizing resonance states dominated the cross section spectrum. Analyses of the experimental profiles yielded resonance strengths and Auger widths. In the 415–440 eV photon region 1s⟶(1s2s22p2 4P)np and 1s⟶(1s2s22p2 2P)np resonances forming well-developed Rydberg series up n=7 and n=8 , respectively, were identified in both the single and double ionization spectra. Theoretical photoionization cross-section calculations, performed using the R-matrix plus pseudo-states (RMPS) method and the multiconfiguration Dirac-Fock (MCDF) approach were bench marked against these high-resolution experimental results. Comparison of the state-of-the-art theoretical work with the experimental studies allowed the identification of new resonance features. Resonance strengths, energies and Auger widths (where available) are compared quantitatively with the theoretical values. Contributions from excited metastable states of the N+ ions were carefully considered throughout.

Strongly coupled plasma effect on excitation energies of O-like ions and photoionization of F-like ions

The main goal of the present study is to analyze and estimate the plasma screening effect on excitation energies O-like ions and photoionization process of F-like ions under the influence of strongly coupled plasma. We have employed an ion sphere model (ISM) in flexible atomic code (FAC) to study and analyze plasma effect in atomic structure of O-like ions and photoionization of F-like ions. We have presented shift in excitation energies of lowest 10 levels of Fe XIX, Co XX, Ni XXI, Cu XXII and Zn XXIII at electron densities ranges 1022–1024 cm−3 under plasma environment. We have also compared our transition wavelengths for Fe XIX with wavelengths observed in ENEA laser facility and calculated from Hebrew University Lawrence Livermore Atomic Code (HULLAC) code at electron density 1021 cm−3. The lowering in ionization potentials and effect on photoionization cross sections for ground and first excited states of Fe XVIII, Co XIX, Ni XX, Cu XXI and Zn XXII also studied at electron densities ranges 1022–1024 cm−3 at five photo-electron energies ranges 100–500 eV.

Theoretical Study of Electronic Structure of Charged Fullerenes

The properties of excited short-living electron quantum levels of positively charged C 60 + Z fullerenes are numerically investigated with the help of the density functional theory (DFT) packages Quantum Espresso, ORCA, and VASP. Earlier, the existence of the volume-localized electron states for neutral and charged fullerenes was demonstrated analytically by making use of the model potential approach based on the unique quasispherical geometrical shape of C60. Here, we revisit this issue by verifying numerically the existence of volume-localized states and by calculating physical parameters of all electronic states with a special focus on highly charged fullerene ions. The ionization potentials of C 60 + Z are calculated and compared with available experimental data. The photoionization cross-sections for neutral fullerene using wave functions are obtained by making use of DFT codes. We demonstrate that lifetimes of excited states vary in the range 10 − 11 ÷ 10 − 4 s, and for the volume-localized levels, lifetimes are longer than those for the surface-localized states.

Valence Photoionization and Autoionization of the Formyl Radical.

We have used 308 nm photolysis of acetaldehyde to measure a photoionization spectrum of the formyl (HCO) radical between 8 and 11.5 eV using an 11 meV FWHM photoionization energy resolution. We have confirmed that the formyl radical is the carrier of the spectrum by generating an identical spectrum of the HCO product in the Cl + H2CO reaction. The spectrum of HCO and its deuterated isotopologue (DCO) have several resolved autoionizing resonances above the Franck-Condon envelope, which we assign to autoionization after initial excitation into neutral 3sσ and 3p Rydberg states converging to the first triplet excited state of HCO+(ã 3A'). The quantum defects for these states are δ3sσ = 1.06 ± 0.02 and δ3p = 0.821 ± 0.019. We report absolute photoionization cross-section measurements of σHCOPI(9.907 eV) = 4.5 ± 0.9 Mb, σHCOPI(10.007 eV) = 4.8 ± 1.0 Mb, σHCOPI(10.107 eV) = 6.0 ± 1.2 Mb, σHCOPI(10.107 eV) = 5.7 ± 1.2 Mb, and σHCOPI(10.304 eV) = 10.6 ± 2.2 Mb relative to the photoionization cross section of the methyl radical. The absolute cross-section measurements are a factor of ∼1.5 larger than those determined in past studies, although the presence of strong autoionizing features supports a dependence on photoionization energy resolution. We propose that the semiempirical model of Xu and Pratt for estimation of free radical photoionization cross sections is more accurate when applied with a reference species containing the same atoms as the free radical rather than isoelectronic species with different atoms.

Double photoionization of atomic oxygen: Feshbach resonances in the two-electron continuum

We describe a joint experimental and theoretical investigation on oxygen double photoionization—the emission of two electrons from atomic oxygen following single photon absorption. High-resolution experimental measurements were performed at the Advanced Light Source, revealing sharp resonance structure superimposed on the more familiar Wannier-like, nearly-linear background. These resonance features are attributed to ionization-plus-excitation Feshbach resonances embedded in the double ionization continuum, doubly-excited states that lie above the double-ionization threshold. Such features are absent in the double photoionization cross section of He, or other quasi-two-electron systems, for which the doubly-ionized atomic core remains inert. For a corresponding theoretical analysis, the R-matrix with pseudostates (RMPS) method was invoked by calculating final-state, two-electron resonances-plus-continua wavefunctions and corresponding single-photon absorption cross sections. Overall agreement is found in the direct, background double photoionization cross section. However, the RMPS method, using a small basis due to practical computational limitations, was unable to reproduce quantitatively the smooth background or the sharper resonance features observed in the measurements, showing instead large-scale oscillations about the experimental background, and characteristic pseudoresonance jitter, associated with an insufficient convergence of the pseudostate representation to the true two-electron infinite series of Feshbach resonances embedded in the two-electron continuum. The prominent resonance structure observed highlights the need to consider multiple excitation processes in atoms more complex than He or quasi-two-electron systems.

Simultaneous effects of temperature, pressure, polaronic mass, and conduction band non-parabolicity on a single dopant in conical GaAs-Al x Ga1–x As quantum dots

This paper is devoted to the theoretical study of the simultaneous effects of temperature, hydrostatic pressure, conduction band non-parabolicity, and polaronic mass on the electronic states and the photoionization cross-section of a shallow donor impurity confined in a GaAs-Al x GaAs conical quantum dot. The calculations have been made within the effective mass approximation. The shallow donor impurity energy levels have been calculated by employing two methods: the variational approach and the finite element method with finite and infinite confining potential. The obtained results suggest that the effects of conduction band non-parabolicity, temperature, hydrostatic pressure, and variation of the conical quantum dot geometries play a significant role in determining of the electronic states system, as well as in the photoionization cross-section. It is also shown that the donor binding energy is very sensitive to temperature and hydrostatic pressure. Indeed, the temperature decreases the donor binding energy while it is increasing with the applied hydrostatic pressure. Also, the quantum dot effective gap is severely affected by the conduction band non-parabolicity. In the case of polaronic mass effects, the present study suggests that they can be omitted without significantly affecting the study’s main conclusions. In this paper, structures with an apical angle ranging from 10° to 150° are approached, allowing simulating quantum dots with a radius of the base much greater than the height and structures with a height much greater than the radius of the base. In the case of hydrostatic pressure and for quantum dots with finite confinement potential, the Γ-X crossover effect has been considered, which is responsible for significant changes in the carriers’ confinement potential.

Experimental validation of theoretically predicted cut-off of L1–L3M4,5 transitions at Z = 50 through measurements of fluorescence and Coster–Kronig yields for Sn and Sb

In the present work, we have deduced the fluorescence (ω 1, ω 2, ω 3) and Coster–Kronig (CK)(f 12, f 13, f 23) yields for Sn (Z = 50) and Sb (Z = 51) from the L i (i = 1–3) sub-shell x-ray intensities measured using the energy tunable synchrotron radiation employing the selective photoionization method. For both the elements, yields have been obtained using two sets of theoretical photoionization cross sections based on the non-relativistic Hartree–Fock–Slater (HFS) model and the self-consistent Dirac–Hartree–Fock (DHF) model. In case of Sb, we have obtained a third set of measured yields also by using the experimental photoionization cross sections evaluated from independent measurements of the mass-attenuation coefficients. The experimental yields for Sb are reported for the first time by us. We have compared the present deduced fluorescence and CK yields with the Dirac–Hartree–Slater model based values, the semi-empirical values tabulated by Krause and the earlier reported values. In case of Sn, using the DHF and the HFS model based photoionization cross sections, two sets of present measured L1 sub-shell fluorescence yields (ω 1) are found to be 0.039 ± 0.007 and 0.036 ± 0.003, and the CK yields (f 13) are found to be 0.428 ± 0.107 and 0.405 ± 0.028, respectively. In case of Sb, using three sets of the photoionization cross sections (DHF, HFS and recent experimental values), the ω 1 values are measured to be 0.042 ± 0.007, 0.040 ± 0.004 and 0.047 ± 0.005, and the CK yields are measured to be 0.343 ± 0.085, 0.297 ± 0.021 and 0.247 ± 0.022, respectively. The comparison of these present measured yields with the theoretical values provided a reliable experimental evidence indicating cut-off of the intense L1–L3M4,5 CK transitions at Z = 50.

Study of high-order harmonic generation in xenon based on time-dependent density-functional theory

The high-order harmonic generation (HHG) in xenon is studied by using the time-dependent density-functional theory. The dynamics of all electrons on the outer 4th and 5th atomic shells is considered with subsequent separation of contributions of different atomic orbitals to the HHG amplitude. It is shown that giant enhancement of HHG yield in a spectral region near 100 eV is caused by perturbation of the electron–electron interaction potential induced by recolliding photoelectron wavepacket originated from the 5p 0 orbital. This perturbation leads to the collective oscillations of all orbitals on the 4th shell closely localized in space and strongly interacting with each other. The resulting HHG yield is enhanced by more than an order of magnitude compared with the response of the single 5p 0 orbital. The high accuracy of the numerical results is confirmed by comparing the calculated HHG spectra and photoionization cross-sections with experimental results and an analytical parameterization of the HHG yield.

Photoionization Cross Section of the NH2 Free Radical in the 11.1-15.7 eV Energy Range.

The NH2 radical is a key component in many astrophysical environments, both in its neutral and cationic forms, being involved in the formation of complex N-bearing species. To gain insight into the photochemical processes into which it operates and to model accurately the ensuing chemical networks, the knowledge of its photoionization efficiency is required, but no quantitative determination has been carried out so far. Combining a flow-tube H-abstraction radical source, a double imaging photoelectron-photoion spectrometer, and a vacuum-ultraviolet synchrotron excitation, the absolute photoionization cross section of the amino radical has been measured in the present work for the first time at two photon energies: σionNH2(12.7 eV) = 7.8 ± 2.2 Mb and σionNH2(13.2 eV) = 7.8 ± 2.0 Mb. These values have been employed to scale the total ion yield previously recorded by Gibson et al. ( J. Chem. Phys. 1985, 83, 4319-4328). The resulting cross section curve spanning the 11.1-15.7 eV energy range will help in refining the current astrophysical models.

Relativistic R-matrix calculations of the photoionization of W63+ ions

The direct and resonant single-photon photoionization of W63+ ions from their ground state 1s 22s 22p 63s 2 S 1/2 and four lowly-excited states 1s 22s 22p 63p 2 P 1/2,3/2 and 1s 22s 22p 63d 2 D 3/2,5/2 has been studied within the framework of the relativistic R-matrix method and the multiconfigurational Dirac–Fock method. Special attention has been paid to obtaining direct and resonant ionization limits and to identifying possible resonant symmetries of W63+ ions. To this end, the photoionization cross-sections have been calculated using the Dirac Atomic R-matrix Code package. Direct and resonant ionization limits were obtained for the ground-state photoionization of W63+ ions, and the resonant peaks identified were found to be associated with the resonances 1s 22s 22p 53lnl′ and 1s 22s2p 63lnl′ (l, l′ = s, p, d) for the fine-structured energy level or configuration at the level of fine structure or configuration. For excited-state photoionization, however, the resonant ionization limits and resonant peaks were hardly distinguishable due to much more densely spaced resonant peaks and a complicated resonant structure, although the respective direct ionization limits are obtained. We expect that this work will remedy the current lack of fundamental studies of the photoionization of W63+ ions and be helpful in the diagnosis and simulation of fusion plasmas in conjunction with the available photoionization data for tungsten ions in other charge states.

Direct double ionization of the Ar+ M shell by a single photon

Author(s): Muller, A; Kilcoyne, ALD; Phaneuf, RA; Holste, K; Schippers, S; Kheifets, AS | Abstract: Direct double ionization of the Ar+(3p-1) ion by a single photon is investigated both experimentally and theoretically. The photon-ion merged-beams technique was employed at the Advanced Light Source in Berkeley, USA, to measure absolute cross sections in the energy range from 60 to 150 eV. In this range, three contributions to the double ionization of Ar+ are to be expected: the removal of two 3p electrons, of a 3s and a 3p electron, and of two 3s electrons. Among the possible mechanisms leading to double ionization, the TS1 (two-step one) process dominates in the near-threshold region. In TS1, a photoelectron is ejected and, on its way out, knocks out a secondary electron. This two-step mechanism is treated theoretically by multiplying the calculated cross section for direct single photoionization of a given subshell with the calculated (e,2e) ionization probability for the ejected photoelectron to knock off a secondary electron. The calculated cross section is in very good agreement with the experiment.

ΔSCF Dyson orbitals and pole strengths from natural ionization orbitals.

The calculation of photoionization cross sections can play a key role in spectral assignments using modeling and simulation. In this work, we provide formal relationships between pole strengths, which are proportional to the photoionization cross section, and terms related to the natural ionization orbital model for ΔSCF calculations. A set of numerical calculations using the developed models is carried out. Pole strength values computed using the two approaches developed for ΔSCF calculations demonstrate excellent agreement with an electron propagator theory model.

Photoionization of open-shell nitrogen confined in C60

Endofullerene photoionization of open-shell N@C60 is investigated using a coupled-channel, correlated R-matrix approach with additional modifications for a finite spherical-shell fullerene potential. Particular focus is on the initial-state dependence of the photoionization cross section. Comparisons show significant differences between the 1s 22s 22p 3(4S) initial state and the metastable 2D and 2P states, as well as strong confinement oscillations.