Fluorescence Time Delay in Multistep Auger Decay as an Internal Clock.

Differences in postcollision interaction (PCI) effects on Kr L_{3}M_{4,5}M_{4,5} Auger electron spectra were observed, depending on whether the initial photoionization occurred slightly above the K threshold or slightly above the L_{3} threshold. For the former, KL fluorescence emission most likely happens and then Auger processes due to the L_{3} hole follow. The time delay due to fluorescence causes a reduced shift of the Auger peak and tailing toward lower energy, since the Auger overtaking of the photoelectron happens later in time and at a location farther away from the ionic core, compared to the case for the simple one-step L_{3}M_{4,5}M_{4,5} Auger decay after L-shell photoionization. Time-dependent theory for PCI in multistep processes agrees well with experiment, illustrating the effect as an internal clock for the time-sequence of the dynamical process.

Resonant inelastic x-ray scattering and photoemission measurement of O2: Direct evidence for dependence of Rydberg-valence mixing on vibrational states in O 1s → Rydberg states.

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.

Dynamics of oxygen Rydberg atom generation following O 1s inner-shell excitation of H2O.

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.

Photodissociation investigation of doubly charged ethanol clusters induced by inner-shell electron ionization.

Fragmentation of doubly charged ethanol clusters [(C(2)H(5)OH)(n)] following the O 1s ionization has been investigated by means of the photoelectron-photoion-photoion coincidence (PEPIPICO) method. The dominant fission channel of (C(2)H(5)OH)(n)(2+) was the formation of protonated cluster ion pairs [H(C(2)H(5)OH)(l)(+)/H(C(2)H(5)OH)(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 (H(3)O(+), C(2)H(5)(+)/COH(+), and C(2)H(4)OH(+)). 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.

Hydrogen bonding in acetone clusters probed by near-edge x-ray absorption fine structure spectroscopy in the carbon and oxygen K-edge regions.

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 C(CO) 1s-->pi( *)(C=O) resonance transition, showed no substantial change in the PIY curves of the acetone clusters, while the C(CH3) 1s-->3ppi(CH(3)) excitation feature was found to be strongly suppressed. The selective suppression of the C(CH3) 1s-->3ppi(CH(3)) resonance transition can be explained by the change in the character of the 3ppi(CH(3)) 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 pi( *)(C=O) resonance of 0.13 eV, because the character of the pi( *)(C=O) orbital remained, regardless of the C=O...H-C hydrogen bonding interaction.

Hydrogen bonding in methanol clusters probed by inner-shell photoabsorption spectroscopy in the carbon and oxygen K-edge regions.

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(CH(3)OH)(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 sigma*(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 sigma*(O-H) resonance transition is interpreted by the change in the character of the sigma*(O-H) molecular orbital at the H-donating OH site due to the hydrogen-bonding interaction.