Photoelectron imaging of helium droplets doped with Xe and Kr atoms

Helium droplets doped with Xe and Kr atoms were photoionized by using VUV synchrotron radiation from the Advanced Light Source and the resulting photoelectron images were measured. A wide range of He droplet sizes, photon energies, and dopant pick-up conditions was investigated. Significant ionization of dopants was observed at 21.6 eV, the absorption maximum of 2p (1)P1 electronic excited state of He droplets, indicating an indirect ionization mechanism via excitation transfer. The photoelectron images and spectra reveal multiple photoionization mechanisms and pathways for the photoelectrons to escape the droplet. Specifically, they show sets of sharp peaks assigned to two mechanisms for Penning ionization of the dopant by He* in which the photoelectrons leave the droplet with no detectable energy loss, a broad, intense feature representing electrons that undergo significant energy loss, and a small amount of ultraslow electrons that may result from electron trapping at the droplet surface. The droplet-size dependence of the broad, intense feature suggests the development of the conduction band edge in the largest droplets seen here ((N) approximately 250,000).     

Photoionization of helium nanodroplets doped with rare gas atoms

Photoionization of He droplets doped with rare gas atoms (Rg=Ne, Ar, Kr, and Xe) was studied by time-of-flight mass spectrometry, utilizing synchrotron radiation from the Advanced Light Source from 10 to 30 eV. High resolution mass spectra were obtained at selected photon energies, and photoion yield curves were measured for several ion masses (or ranges of ion masses) over a wide range of photon energies. Only indirect ionization of the dopant rare gas atoms was observed, either by excitation or charge transfer from the surrounding He atoms. Significant dopant ionization from excitation transfer was seen at 21.6 eV, the maximum of He 2p 1P absorption band for He droplets, and from charge transfer above 23 eV, the threshold for ionization of pure He droplets. No Ne+ or Ar+ signal from droplet photoionization was observed, but peaks from HenNe+ and HenAr+ were seen that clearly originated from droplets. For droplets doped with Rg=Kr or Xe, both Rg+ and HenRg+ ions were observed. For all rare gases, Rg2+ and HenRgm+ (n,m> or =1) were produced by droplet photoionization. Mechanisms of dopant ionization and subsequent dynamics are discussed.     

Two-color visible/vacuum ultraviolet photoelectron imaging dynamics of Br2

An experimental two-color photoionization dynamics study of laser-excited Br2 molecules is presented, combining pulsed visible laser excitation and tunable vacuum ultraviolet (VUV) synchrotron radiation with photoelectron imaging. The X 1Sigmag + -B 3Pi0+u transition in Br2 is excited at 527 nm corresponding predominantly to excitation of the v' = 28 vibrational level in the B 3Pi0+u state. Tunable VUV undulator radiation in the energy range of 8.40-10.15 eV is subsequently used to ionize the excited molecules to the X 2Pi32,12 state of the ion, and the ionic ground state is probed by photoelectron imaging. Similar experiments are performed using single-photon synchrotron ionization in the photon energy range of 10.75-12.50 eV without any laser excitation. Photoelectron kinetic energy distributions are extracted from the photoelectron images. In the case of two-color photoionization using resonant excitation of the intermediate B 3Pi0+u state, a broad distribution of photoelectron kinetic energies is observed, and in some cases even a bimodal distribution, which depends on the VUV photon energy. In contrast, for single-photon ionization, a single nearly Gaussian-shaped distribution is observed, which shifts to higher energy with photon energy. Simulated spectra based on Franck-Condon factors for the transitions Br2(X 1Sigmag+, v" = 0)-Br2 +(X 2Pi12,32, v+) and Br2(B 3Pi0+u, v' = 28)-Br2 +(X 2Pi12,32, v+) are generated. Comparison of these calculated spectra with the measured images suggests that the differences in the kinetic energy distributions for the two ionization processes reflect the different extensions of the vibrational wave functions in the v" = 0 electronic ground state (X 1Sigmag+) versus the electronically and vibrationally excited state (B 3Pi0+u, v' = 28).     

Femtosecond photoelectron imaging of transient electronic states and Rydberg atom emission from electronically excited he droplets

Ultrafast relaxation of electronically excited pure He droplets is investigated by femtosecond time-resolved photoelectron imaging. Droplets are excited by extreme ultraviolet (EUV) pulses with photon energies below 24 eV. Excited states and relaxation products are probed by ionization with an infrared (IR) pulse with 1.6 eV photon energy. An initially excited droplet state decays on a time scale of 220 fs, leading predominantly to the emission of unaligned 1s3d Rydberg atoms. In a second relaxation channel, electronically aligned 1s4p Rydberg atoms are emitted from the droplet within less than 120 fs. The experimental results are described within a model that approximates electronically excited droplet states by localized, atomic Rydberg states perturbed by the local droplet environment in which the atom is embedded. The model suggests that, below 24 eV, EUV excitation preferentially leads to states that are localized in the surface region of the droplet. Electronically aligned 1s4p Rydberg atoms are expected to originate from excitations in the outermost surface regions, while nonaligned 1s3d Rydberg atoms emerge from a deeper surface region with higher local densities. The model is used to simulate the He droplet EUV absorption spectrum in good agreement with previously reported fluorescence excitation measurements.     

Electron emission from naphthacene crystal due to the impact of argon and krypton metastable atoms

Energy distributions of electrons emitted from polycrystalline naphthacene due to the impact of metastable argon or krypton atoms were measured. The energy distribution peaks, except for large peaks appearing near zero eV, correspond to the kinetic energies estimated from photoelectron spectra on the assumption that the excitation energies of the metastable atoms are transferred to the electrons in the valence bands. The results are interpreted as the occurrence of Penning ionization (Auger de-excitation) on the naphthacene surface.     

Valence and inner-valence shell dissociative photoionization of CO in the 26-33 eV range. II. Molecular-frame and recoil-frame photoelectron angular distributions

Experimental and theoretical results for molecular-frame photoemission are presented for inner-valence shell photoionization of the CO molecule induced by linearly and circularly polarized light. The experimental recoil frame photoelectron angular distributions (RFPADs) obtained from dissociative photoionization measurements where the velocities of the ionic fragment and photoelectron were detected in coincidence, are compared to RFPADs computed using the multichannel Schwinger configuration interaction method. The formalism for including a finite lifetime of the predissociative ion state is presented for the case of general elliptically polarized light, to obtain the RFPAD rather than the molecular frame photoelectron angular distribution (MFPAD), which would be obtained with the assumption of instantaneous dissociation. We have considered photoionization of CO for the photon energies of 26.0 eV, 29.5 eV, and 32.5 eV. A comparison of experimental and theoretical RFPADs allows us to identify the ionic states detected in the experimental studies. In addition to previously identified states, we found evidence for the 2 (2)Δ state with an ionization potential of 25.3 eV and (2)Σ(+) states with ionization potentials near 32.5 eV. A comparison of the experimental and theoretical RFPADs permits us to estimate predissociative lifetimes of 0.25-1 ps for some of the ion states. Consideration of the MFPADs of a series of (2)Π ion states indicates the importance of inter-channel coupling at low photoelectron kinetic energy and the limitations of a single-channel analysis based on the corresponding Dyson orbitals.     

The interaction of slow positrons with organic moecules above and below positronium formation thresholds

A review is given of the ionization of organic moecules by monoenergetic positrons having energies in the range of 0.5–15 eV. Two mechanisms, unique to positrons, are described. If the kinetic energy of the positron is above the positronium formation threshold, such that electrons can be removed from the molecules to form free positronium atoms, the ionization/fragmentation behavior can be explained qualitatively by a modification of the Ore gap theory. To explain how positrons can ionize and fragment molecules when their kinetic energies are below the positronium formation threshold, it is necessary to assume that energy is transferred to the molecule by the annihilation process. Ionization cross sections for positrons having kinetic energies below the positronium formation threshold are sensitive to molecular size, structure and bond types. Continuing work involves a search for positronium compound formation and measurements of the kinetic energy distributions of ions.     

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.     

Near-threshold photoionization of hot isopropyl radicals

A combination of ion imaging and vacuum ultraviolet, single-photon ionization is used to study the internal energy dependence of the photoionization cross section of isopropyl radicals produced by the 266 nm photodissociation of isopropyl iodide. The isopropyl radicals so produced have internal energies of approximately 0.3-2.0 eV. Images recorded for photoionization energies from just below the adiabatic ionization threshold at 7.37+/-0.02 and 8.04 eV are essentially identical both to each other and to that recorded at 9.67 eV. These results imply that the photoionization cross section is only weakly dependent on internal energy. Several factors contributing to this observation are discussed, as are the implications for the photoionization of other systems with significant internal excitation.     

Photoelectron spectroscopy and thermochemistry of tert-butylisocyanide-substituted cobalt tricarbonyl nitrosyl

A new organometallic complex, Co(CO)2NOtBuNC, was synthesized and investigated by photoelectron spectroscopy (PES) and threshold photoelectron photoion coincidence (TPEPICO) spectrometry in order to determine its ionization energy as well as the bond energies in the ionic forms. The assignment of the nine peaks in the PES was based on Kohn-Sham molecular orbital energies, and an adiabatic ionization energy of 7.30 +/- 0.05 eV was determined. In the TPEPICO experiment, the following 0 K onsets were determined for the various fragment ions: CoCONOtBuNC+ (8.17 +/- 0.05 eV); CoNOtBuNC+ (9.01 +/- 0.05 eV); and CotBuNC+ (10.42 +/- 0.05 eV). Because the photon source did not extend above 14 eV, we could not observe the bare Co+ ion in the experiment. The heat of formation of the CotBuNC+ ion was estimated by ab initio and DFT calculations of the CoL+ + tBuNC --> CotBuNC+ + L (L = CO, NO, NH3, H2O, PMe3) substitution enthalpies.     

Experimental and quantum-chemical studies on photoionization and dissociative photoionization of CH2Br2

The dissociative photoionization of CH2Br2 in a region approximately 10-24 eV was investigated with photoionization mass spectroscopy using a synchrotron radiation source. An adiabatic ionization energy of 10.25 eV determined for CH2Br2 agrees satisfactorily with predictions of 10.26 and 10.25 eV with G2 and G3 methods, respectively. Observed major fragment ions CH2Br+, CHBr+, and CBr+ show appearance energies at 11.22, 12.59, and 15.42 eV, respectively; minor fragment ions CHBr2+, Br+, and CH2+ appear at 12.64, 15.31, and 16.80 eV, respectively. Energies for formation of observed fragment ions and their neutral counterparts upon ionization of CH2Br2 are computed with G2 and G3 methods. Dissociative photoionization channels associated with six observed fragment ions are proposed based on comparison of determined appearance energies and predicted energies. An upper limit of DeltaH0f,298(CHBr+) < or = 300.7 +/- 1.5 kcal mol(-1) is derived experimentally; the adiabatic ionization energy of CHBr is thus derived to be < or = 9.17 +/- 0.23 eV. Literature values for DeltaH0f,298(CBr+) = 362.5 kcal mol(-1) and ionization energy of 10.43 eV for CBr are revised to be less than 332 kcal mol(-1) and 9.11 eV, respectively. Also based on a new experimental ionization energy, DeltaH0f,298(CH2Br2+) is revised to be 236.4 +/- 1.5 kcal mol(-1).     

Dissociative double photoionization of N2 using synchrotron radiation: appearance energy of the N2+ dication

Photoionization cross sections for the production of the doubly charged ion N2+ from N2 have been measured by means of synchrotron radiation in the photon energy range from 50 to 110 eV. The appearance energy for N2+ has been determined as 55.2+/-0.2 eV, i.e., about 1.3 eV higher than the spectroscopic dissociation limit leading to the charge asymmetric dissociation channel N2+(2P)+N(4S) at 53.9 eV. The onset of a second threshold at 59.9+/-0.2 eV is detected and the energy dependence of photoion intensities near the threshold regions is interpreted in terms of the Wannier theory. The production of the N2+ dication is discussed in terms of direct and indirect mechanisms for dissociative charge asymmetric photoionization and by comparison with the potential energy curves of the intermediate N(2)2+ dication. Experimental evidences for the opening of the Coulomb explosion channel N2++N+ at high photon energies are provided by measuring the kinetic energy release spectra of N2+ fragments at selected photon energies.     

Threshold photoionization behaviour of (Li2O)Lin clusters produced by a laser vaporization source

We report on the production of small and medium size lithium and lithium oxide clusters by a laser vaporization cluster source. The isotopomeric distribution of natural lithium allowed to identify Li_kO clusters as the most abundant components in the mass spectrum. Photoionization efficiency curves of Li_kO clusters with photon energies from 3.4 to 4.7 eV were measured for 8 ≤ k ≤ 27. Using linear extrapolation of the increase in photoionization efficiency with photon energy, ionization potentials were extracted. With the chemical bond of the O^2- anion to two Li atoms, leaving n = k-2 valence electrons in the (Li₂O)Li_n clusters, clear shell closure effects are present at n = 8 and n = 20.     

Thermal vaporization of biological nanoparticles: fragment-free vacuum ultraviolet photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene

A simple, new way to introduce fragile biomolecules into the gas phase via thermal vaporization of nanoparticles is described. The general utility of this technique for the study of biomolecules is demonstrated by coupling this source to tunable synchrotron vacuum ultraviolet radiation. Fragment-free photoionization mass spectra of tryptophan, phenylalanine-glycine-glycine, and beta-carotene are detected with signal-to-noise ratios exceeding 100. The 8.0 eV photoionization mass spectrum of tryptophan nanoparticles vaporized at 373 K is dominated by a single parent ion peak that exhibits a 20-fold enhancement over the methylene indole fragment ion. The degree of dissociative photoionization of tryptophan can be precisely controlled either by the thermal energy imparted into the neutral tryptophan molecule or by the energy of the ionizing photon. The results reveal how approximately 0.5 eV changes in internal energy affect both the photoionization mass spectrum of tryptophan and the appearance energy of the daughter ion fragments. This method allows the ionization energies of glycine (9.3 +/- 0.1 eV), tryptophan (7.3 +/- 0.2 eV), phenylalanine (8.6 +/- 0.1 eV), phenylalanine-glycine-glycine (9.1 +/- 0.1 eV), and beta-carotene (<7.0 eV) molecules to be determined directly from the photoionization efficiency spectra.     

Absolute photoionization cross section of the ethyl radical in the range 8-11.5 eV: synchrotron and vacuum ultraviolet laser measurements

The absolute photoionization cross section of C(2)H(5) has been measured at 10.54 eV using vacuum ultraviolet (VUV) laser photoionization. The C(2)H(5) radical was produced in situ using the rapid C(2)H(6) + F → C(2)H(5) + HF reaction. Its absolute photoionization cross section has been determined in two different ways: first using the C(2)H(5) + NO(2) → C(2)H(5)O + NO reaction in a fast flow reactor, and the known absolute photoionization cross section of NO. In a second experiment, it has been measured relative to the known absolute photoionization cross section of CH(3) as a reference by using the CH(4) + F → CH(3) + HF and C(2)H(6) + F → C(2)H(5) + HF reactions successively. Both methods gave similar results, the second one being more precise and yielding the value: σ(C(2)H(5))(ion) = (5.6 ± 1.4) Mb at 10.54 eV. This value is used to calibrate on an absolute scale the photoionization curve of C(2)H(5) produced in a pyrolytic source from the C(2)H(5)NO(2) precursor, and ionized by the VUV beam of the DESIRS beamline at SOLEIL synchrotron facility. In this latter experiment, a recently developed ion imaging technique is used to discriminate the direct photoionization process from dissociative ionization contributions to the C(2)H(5)(+) signal. The imaging technique applied on the photoelectron signal also allows a slow photoelectron spectrum with a 40 meV resolution to be extracted, indicating that photoionization around the adiabatic ionization threshold involves a complex vibrational overlap between the neutral and cationic ground states, as was previously observed in the literature. Comparison with earlier photoionization studies, in particular with the photoionization yield recorded by Ruscic et al. is also discussed.     

Collision-energy-resolved Penning ionization electron spectroscopy of bromomethanes (CH3Br, CH2Br2, and CHBr3) by collision with He*(2(3)S) metastable atoms

Ionization of bromomethanes (CH3Br, CH2Br2, and CHBr3) upon collision with metastable He*(2(3)S) atoms has been studied by means of collision-energy-resolved Penning ionization electron spectroscopy. Lone-pair (nBr) orbitals of Br4p characters have larger ionization cross sections than sigma(C-Br) orbitals. The collision-energy dependence of the partial ionization cross sections shows that the interaction potential between the molecule and the He*(2(3)S) atom is highly anisotropic around CH3Br or CH2Br2, while isotropic attractive interactions are found for CHBr3. Bands observed at electron energies of approximately 2 eV in the He*(2(3)S) Penning ionization electron spectra (PIES) of CH2Br2 and CHBr3 have no counterpart in ultraviolet (He I) photoionization spectra and theoretical (third-order algebraic diagrammatic construction) one-electron and shake-up ionization spectra. Energy analysis of the processes involved demonstrates that these bands and further bands overlapping with sigma(C-Br) or piCH2 levels are related to autoionization of dissociating (He+ - Br-) pairs. Similarly, a band at an electron energy of approximately 1 eV in the He*(2(3)S) PIES spectra of CH3Br has been ascribed to autoionizing Br** atoms released by dissociation of (unidentified) excited states of the target molecule. A further autoionization (S) band can be discerned at approximately 1 eV below the lone-pair nBr bands in the He*(2(3)S) PIES spectrum of CHBr3. This band has been ascribed to the decay of autoionizing Rydberg states of the target molecule (M**) into vibrationally excited states of the molecular ion. It was found that for this transition, the interaction potential that prevails in the entrance channel is merely attractive.     

Photoionization cross-section weighted DFT simulations as promising tool for the investigation of the electronic structure of open shell metal-phthalocyanines

The valence band structure of different metal-phthalocyanines was investigated by comparing ultraviolet photoelectron spectra at different excitation energies with simulated spectra that take the different photoionization cross-sections at these energies into account. The Kohn-Sham eigenvalue spectra, derived from density functional theory calculations, using hybrid exchange-correlation functionals, were weighted with the photoionization coefficients in accordance with the used excitation energy. By applying these techniques, the differences in the photoelectron spectra using He I and He II radiation can be reproduced and investigated. It will be shown that the 3d-orbitals of the used metal central atom of these molecules have a major influence. The changes at different excitation energies were studied for Fe, Co, and Cu central atoms to describe the chemical tailoring effects.     

Photoelectron spectroscopy of naphthacene and perylene crystals by the rare gas emission lines

The energy distribution curves (EDC's) of the photoelectrons emitted from naphthacene (C₁₈H₁₂) and perylene (C₂₀H₁₂) crystals were measured using the rare gas resonance emission lines (He 21.22 eV, Ne 16.85 and 16.67 eV and Ar 11.83 and 11.62 eV). The peaks in the higher kinetic energy regions agree well with the peaks obtained from molecular photoelectron spectroscopy studies if constant energy shifts are assumed. In the lower kinetic energy regions, however, fixed kinetic energy peaks are found which are independent of the incident photon energies.     

Ultraviolet photoelectron spectroscopy study of the thermochromic phase transition in urethane-substituted polydiacetylenes

Threshold solid-state ionization energies determined from ultraviolet photoelectron spectra are reported for the thermochromic polydiacetylenes (PDAs) from the bis-ethyl- and bis-n-propyl urethanes of 5,7-dodecadiyn-1,12-diol (ETCD and PUDO, respectively) and the nonthermochromic 1,6-bis-p-toluenesulfonate of 2,4-hexadiyne-1,6-diol (PTS) at temperatures above and below the thermochromic phase transition. PDA-PTS has an ionization energy of 5.66 eV which does not change significantly as the temperature is raised above 140 degrees C. At 25 degrees C, PDA-ETCD and PDA-PUDO have threshold ionization energies of 5.65 and 5.51 eV, respectively. The ionization energies of these PDAs increase by approximately 0.34 eV as temperature is raised above 140 degrees C and returns to the lower values as temperature is reduced to 25 degrees C. The magnitude of the increase in ionization energy on heating to temperatures above the thermochromic transition is very close to the shift in energy of the electronic spectrum over the same temperature range. These observations suggest that the structural changes that take place in the course of the thermochromic transition are primarily associated with the valence band and are consistent with partial relief of mechanical strains.     

Absolute dipole oscillator strengths for photoabsorption,photoionization and ionic photofragmentation processes in HBr

Absolute dipole oscillator strengths (cross section) have been obtained for valence shell photoabsorption (7–100eV) and a variety of partial photoionization (11–40 eV) processes in gaseous HBr. Partial dipole oscillator strengths are reported for the formation of the X²Π, A²Σ⁺ and B²Σ electronic state of HBr⁺ as well as the respective photoelectron branching ratios. The photoelectron binding energy spectra show clear evidence of many-body effects in photoionization to the B²Σ state of HBr⁺ with the ionization oscillator strength divided over many bands as predicted by many-body Green's function calculations. Partial dipole oscillator strengths are also reported for molecular ion formation as well as for all dissociative ionization processes. The measurements have been made by the dipole (e,e) (e,2e) and (e,e + ion) methods, which respectively provide quantitative measurements of photoabsorption, photoelectron spectroscopy and photoionization mass spectrometry at continuously tuneable energies. The measurements of dipole oscillator strengths for production of electronic states of HBr⁺ are combined with those for molecular and dissociative photoionization. These, considered together with the ionization and appearance potentials, provide a quantitative dipole breakdown picture for the ionic photofragmentation pathways of HBr in the energy region up to 40 eV.