Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface

Vibration dependent branching and photoelectron angular distributions observed across the Cooper minimum region of bromobenzene

Vibrational state-resolved photoelectron anisotropy parameters, beta, for the ~X 2B1, ~B 2B2, and ~C2B1 state ionizations of bromobenzene have been recorded at photon energies ranging from 20.5 to 94 eV, so spanning the region of the expected bromine Cooper minimum (CM). The ~X state displays no CM and its beta value is also independent of vibrational level, in accord with the Franck-Condon Approximation. The ~B and ~ C state beta values display the CM to differing degrees, but both show a vibrational dependence that extends well below the obvious CM dip. Calculations are presented that replicate these observations of Franck-Condon Approximation breakdown spanning an extended photon energy range. This is the first demonstration of such wide-ranging breakdown detected in the beta anisotropy parameter in the absence of any resonance. Measured and calculated vibrational branching ratios for these states are also presented. Although the ~B state branching ratios remain constant, in accord with Franck-Condon expectations, the ~X and (especially) the ~C state ratios display weak, quasi-linear variations across the studied range of photon energy, but with no apparent correlation with the CM position

An experimental and theoretical study of the valence shell photoelectron spectrum of oxalyl chloride

Polarization dependent photoelectron spectra encompassing the outer valence orbitals of oxalyl chloride have been recorded in the photon energy range 19 – 91 eV. These have allowed photoelectron anisotropy parameters and branching ratios to be determined. Photoionization partial cross sections and photoelectron anisotropy parameters have been calculated with the Continuum Multiple Scattering – Xα approach. Four of the outer valence orbitals are predicted to possess a significant Cl 3p lone-pair character and have closely grouped binding energies. The photoionization dynamics of these four orbitals are predicted to be strongly affected by the Cooper minimum associated with the Cl 3p orbital in the isolated atom at photon energies around 40 eV. A comparison between the theoretical and measured photoelectron anisotropy parameters has enabled the molecular orbital sequence to be clarified. A doublet has been observed in the region of the photoelectron spectrum where a band due to the 5bu orbital might be anticipated. Our calculations indicate that the 6bu and 5bu orbitals are coupled. This coupling may account for the apparent lack of a pronounced Cooper minimum in the β-parameter associated with the nominal 6bu ionization and for the unexpected appearance of the adjacent photoelectron band, nominally associated with the 5bu orbital. The vertical ionization energy of the outermost 7ag orbital was experimentally determined to be 11.266±0.005 eV

From synchrotrons for XFELs : The soft x-ray near-edge spectrum of the ESCA molecule

A predictive understanding of soft x-ray near-edge absorption spectra of small molecules is an enduring theoretical challenge and of current interest for x-ray probes of molecular dynamics. We report the experimental absorption spectrum for the electron spectroscopy for chemical analysis (ESCA) molecule (ethyl trifluoroacetate) near the carbon 1s absorption edge between 285-300 eV. The ESCA molecule with four chemically distinct carbon sites has previously served as a theoretical benchmark for photoelectron spectra and now for photoabsorption spectra. We report a simple edge-specific approach for systematically expanding standard basis sets to properly describe diffuse Rydberg orbitals and the importance of triple excitations in equation-of-motion coupled-cluster calculations of the energy interval between valence and Rydberg excitations

Valence shell photoelectron angular distributions and vibrationally resolved spectra of imidazole: A combined experimental–theoretical study

Linearly polarized synchrotron radiation has been used to record polarization dependent valence shell photoelectron spectra of imidazole in the photon energy range 21-100 eV. These have allowed the photoelectron angular distributions, as characterized by the anisotropy parameter β, and the electronic state intensity branching ratios to be determined. Complementing these experimental data, theoretical photoionization partial cross sections and β-parameters have been calculated for the outer valence shell orbitals. The assignment of the structure appearing in the experimental photoelectron spectra has been guided by vertical ionization energies and spectral intensities calculated by various theoretical methods that incorporate electron correlation and orbital relaxation. Strong orbital relaxation effects have been found for the 15a′, nitrogen lone-pair orbital. The calculations also predict that configuration mixing leads to the formation of several low-lying satellite states. The vibrational structure associated with ionization out of a particular orbital has been simulated within the Franck-Condon model using harmonic vibrational modes. The adiabatic approximation appears to be valid for the X 2A″ state, with the β-parameter for this state being independent of the level of vibrational excitation. However, for all the other outer valence ionic states, a disparity occurs between the observed and the simulated vibrational structure, and the measured β-parameters are at variance with the behavior expected at the level of the Franck-Condon approximation. These inconsistencies suggest that the excited electronic states may be interacting vibronically such that the nuclear dynamics occur over coupled potential energy surfaces

The role of intramolecular scattering in K-shell photoionization

We report evidence of intramolecular scattering occurring in inner shell photoionization of small molecules. Pronounced oscillations of the ratios between vibrationally resolved cross sections (v-ratios) as a function of photon energy have been observed theoretically and experimentally. Qualitative agreement with a 1st Born model confirms that they are due to intramolecular scattering: when an electron is ejected from a very localized region in the center of a polyatomic molecule, such as the C(1s) orbital in a CF4 molecule, it is diffracted by the surrounding atomic centers, encoding the geometry of the molecule [1, 2]

Vibrationally resolved B 1s photoionization cross section of BF3

We present a study of the vibrationally resolved B 1s photoionization cross section of the BF 3 molecule. A combination of high-resolution photoelectron spectroscopy measurements and of state-of-the-art calculations shows the evolution of the photon energy dependence of the cross section from a complete trapping of the photoelectron wave (low energies) to oscillations due to intramolecular scattering. These diffraction patterns allow to access structural information of both the neutral molecule and the core -hole species generated upon photoabsoptio