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High-resolution resonant inelastic x-ray scattering (RIXS) and low-energy photoemission spectra of oxygen molecules have been measured for investigating the electronic structure of Rydberg states in the O 1s →σ* energy region. The electronic characteristics of each Rydberg state have been successfully observed, and new assignments are made for several states. The RIXS spectra clearly show that vibrational excitation is very sensitive to the electronic characteristics because of Rydberg-valence mixing and vibronic coupling in O2. This observation constitutes direct experimental evidence that the Rydberg-valence mixing characteristic depends on the vibrational excitation near the avoided crossing of potential surfaces. We also measured the photoemission spectra of metastable oxygen atoms (O*) from O2 excited to 1s → Rydberg states. The broadening of the 4p Rydberg states of O* has been found with isotropic behavior, implying that excited oxygen molecules undergo dissociation with a lifetime of the order of 10 fs in 1s → Rydberg states. [ABSTRACT FROM AUTHOR]

The dissociative dynamics of the K shell excited ozone were studied by time-of-flight (TOF) mass spectrometry of fragment ions. The TOF spectra were obtained at 0 and 90 degrees relative to the electric vector of linearly polarized soft X-ray. In the K shell excitation at 529 eV photoabsorption peak, the energetic O+ fragment ion was ejected anisotropically, while at the 536 eV band, it was isotropic. The beta values obtained from simulation of the TOF spectra were in agreement with the previous assignments that the 529 eV band is the pi*

The dissociation and ionization dynamics of CF3I and CH3I molecules were investigated using a pump-and-probe technique that employs a soft x-ray free-electron laser (SACLA) in Japan. First, time-resolved inner-shell photoelectron spectroscopy was employed to observe the ultrafast reaction of CF3I by monitoring iodine 4d electrons. The change in the I 4d state observed in the photoelectron spectra is found to occur with a rise time τ of approximately 40 fs after a pump laser pulse, which is faster than that observed when an ultrafast gas-phase electron diffraction technique is employed. This implies that the inner-shell photoelectron spectroscopy is more sensitive to the potential surface near the Franck–Condon region. Second, a strong laser intensity at 266 nm, corresponding to a power density of 1.9 × 1014 W cm−2, can easily ionize CH3I molecules via multiphoton ionization processes, and the time dependence of the valence photoelectron spectra clearly shows that at the picosecond timescale, this pump laser pulse causes spectral peaks to shift owing to space-charge effects in response to the large amount of ions generated. Thus, the SACLA can be a useful tool to investigate not only the dynamical process of molecular dissociation but also the ionization process through the shift in the peaks of photoelectron spectra. [ABSTRACT FROM AUTHOR]

The emission of low-energy electrons from H2O has been investigated at photon excitation energies in the vicinity of the O 1s ionization threshold. Neutral oxygen Rydberg atoms (O*) were found to form, and the correlation between the initial inner-shell excited state of H2O and the Rydberg state of O* was determined. The initially excited electron in a Rydberg orbital is shown to remain associated with O* even after the cleavage of two O-H bonds.We also show that the energy discrepancy between two Rydberg states of H2O and O* can be explained by the influence of the post-collision interaction, which becomes stronger as the excitation energy approaches the 1s ionization threshold. [ABSTRACT FROM AUTHOR]

Fragmentation of doubly charged ethanol clusters [(C2H5OH)n] following the O 1s ionization has been investigated by means of the photoelectron-photoion-photoion coincidence (PEPIPICO) method. The dominant fission channel of (C2H5OH)n2+ was the formation of protonated cluster ion pairs [H(C2H5OH)l+/H(C2H5OH)m+]. The fragmentation mechanisms of these ion pairs were discussed based on the analysis of the PEPIPICO contour shape. It was clarified that the prominent fragmentation channel was a secondary decay mechanism, where neutral evaporation occurs after charge separation. On the other hand, the formation of small fragment ions was suppressed, excluding the formation of certain specific fragments (H3O+, C2H5+/COH+, and C2H4OH+). The formation of small fragment ions was suppressed due to the cooling effect caused by the neutral evaporation and the decrease in the electrostatic repulsive force caused by charge separation. [ABSTRACT FROM AUTHOR]

Hydrogen bonding in acetone clusters was investigated using near-edge x-ray absorption fine structure (NEXAFS) spectroscopy and density functional theory calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of the cluster ions were measured as the NEXAFS spectra of acetone clusters. In the carbon K-edge region, the first resonance peak, which was assigned to the CCO 1s→π*(C=O) resonance transition, showed no substantial change in the PIY curves of the acetone clusters, while the CCH3 1s→3pπ(CH3) excitation feature was found to be strongly suppressed. The selective suppression of the CCH3 1s→3pπ(CH3) resonance transition can be explained by the change in the character of the 3pπ(CH3) orbital due to the C=O...H–C type of hydrogen-bonding interaction. On the other hand, the NEXAFS spectra of the acetone molecule and clusters were almost identical in the oxygen K-edge region, except for a small shift in the π*(C=O) resonance of 0.13 eV, because the character of the π*(C=O) orbital remained, regardless of the C=O...H–C hydrogen bonding interaction. [ABSTRACT FROM AUTHOR]

Hydrogen bonding in methanol clusters has been investigated by using inner-shell photoabsorption spectroscopy and density functional theory (DFT) calculations in the carbon and oxygen K-edge regions. The partial-ion-yield (PIY) curves of H(CH3OH)n+ were measured as the soft x-ray absorption spectra of methanol clusters. The first resonance peak in the PIY curves, which is assigned to the σ*(O–H) resonance transition, exhibits a 1.20 eV blueshift relative to the total-ion-yield (TIY) curves of molecular methanol in the oxygen K-edge region, while it exhibits a shift of only 0.25 eV in the carbon K-edge region. Decreased intensities of the transitions to higher Rydberg orbitals were observed in the PIY curves of the clusters. The drastic change in the σ*(O–H) resonance transition is interpreted by the change in the character of the σ*(O–H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction. [ABSTRACT FROM AUTHOR]

The photodissociation of O3 in the Hartley band has been investigated by high-resolution photofragment translational spectroscopy (PTS). At λdiss=248 nm we determined the quantum yield of the dominant decay channel leading to O2(1Δg)+O(1D) and the fragment vibrational state distribution. The fragment recoil anisotropy (β=1.25±0.15) was found to be independent of the fragment vibrational states. Between λdiss=275 and 295 nm β assumes a value of 1.6±0.2, which exceeds the value expected for a simple impulsive process. Photofragment yield measurements carried out by PTS between 272 and 286 nm revealed a strong fluctuation of the vibrational state distribution with λdiss. Based on the small but distinct structure superimposed on the broad continuum of the Hartley band and the findings of recent 3D wave packet calculations, we propose this fluctuation, a manifestation of wavelength-dependent partial cross sections, to arise predominantly from an interference effect. The latter occurs between the part of the initially prepared wavepacket which propagates directly into the exit channel and a (minor) part which is temporarily trapped by the motion of the bending and symmetric stretching modes in the excited O3 molecule. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]