Probing molecular bond-length using molecular-frame photoelectron angular distributions.

The molecular-frame photoelectron angular distributions (MFPADs) in O 1s photoemission from CO2 molecule were measured. Patterns due to photoelectron diffractions were observed in the MFPADs. The polarization-averaged MFPADs were compared with theoretical calculation and were found to be useful in determining the molecular bond-length, which is a component to determine molecular structures.

Formation of hot hydrogen atoms from superexcited states of acetylene.

The cross sections for the formation of the H(2p) and H(2s) atoms, σ 2p and σ 2s , respectively, in photoexcitation of C2H2 were obtained in an absolute scale for studying formation and decay of superexcited states in the extreme ultraviolet range. Several superexcited states of C2H2 including multiply excited states were found in the curve of the σ 2p cross sections as a function of the incident photon energy. The same states seem to contribute to the variation in the σ 2s cross sections as well, which can be ascribed to the non-adiabatic transitions between the 2p and 2s channels. The Σ/Π symmetry-resolved cross sections for the H(2s) atom formation, σ 2 s Σ and σ 2 s Π , were also obtained on an absolute scale. The coupling between the Σ u + 1 and 1Π u states was found to be small.

Site-dependent Si KL23L23 resonant Auger electron spectra following inner-shell excitation of Cl3SiSi(CH3)3.

Spectator resonant Auger electron spectra with the Si 1s photoexcitation of Cl3SiSi(CH3)3 have been measured using an electron spectroscopic technique combined with undulator radiation. The transition with the highest intensity in the total ion yield (TIY) spectrum, coming from excitation of a Si 1s electron on the Cl-side into a vacant valence orbital, generates the resonant Auger decay in which the excited electron remains in this valence orbital. Photoexcitation of 1s electrons into some Rydberg orbitals induces Auger shake-down transitions, because higher-lying Rydberg orbitals in the two Si atoms closely positioned hold spatially overlapping considerably. A broad TIY peak slightly above the 1s ionization thresholds appreciably yields resonant Auger decays in which a slow photoelectron is re-captured into a higher-lying Rydberg orbital. The normal Auger peak shape at this photon energy is distorted due to a post-collision interaction effect. These findings provide a clear understanding on properties of the excited orbitals which are ambiguous in the measurement of the TIY only.

Cross sections for the formation of H(n = 2) atom via superexcited states in photoexcitation of methane and ammonia.

The absolute cross sections for the formation of the H(2s) and H(2p) atoms, σ2s and σ2p, respectively, in photoexcitation of CH4 and NH3 were measured in the range of the incident photon energy 15-48 eV for studying superexcited states of the molecules. The same superexcited states were found to contribute to the σ2s and σ2p cross sections. It was concluded that the non-adiabatic transitions play a significant role during the dissociation of the superexcited states and ionic states.

A study to control chemical reactions using Si:2p core ionization: site-specific fragmentation.

In an aim to create a "sharp" molecular knife, we have studied site-specific fragmentation caused by Si:2p core photoionization of bridged trihalosilyltrimethylsilyl molecules in the vapor phase. Highly site-specific bond dissociation has been found to occur around the core-ionized Si site in some of the molecules studied. The site specificity in fragmentation and the 2p binding energy difference between the two Si sites depend in similar ways on the intersite bridge and the electronegativities of the included halogen atoms. The present experimental and computational results show that for efficient "cutting" the following conditions for the two atomic sites to be separated by the knife should be satisfied. First, the sites should be located far from each other and connected by a chain of saturated bonds so that intersite electron migration can be reduced. Second, the chemical environments of the atomic sites should be as different as possible.

A new spectroscopic method for resolving the electronic symmetry properties of the highly excited molecules produced in photoexcitation.

A novel method of spectroscopy for highly excited states of molecules in the valence excitation range has been established through the detection of metastable hydrogen atoms in the 2s state formed by photoexcitation. The detector for the metastable hydrogen atom is composed of a stack of parallel plate electrodes that creates a localized electric field and triggers the emission of the Lyman-alpha photon from the atom and a chevron pair of microchannel plates that detects the photon. For linear molecules, the angle-resolved detection of the metastable hydrogen atom enables us to measure cross sections in which electronic symmetries of highly excited molecular states are resolved. Such symmetry-resolved cross section measurements were carried out for doubly excited states of H(2).

Large pressure effect on the angular distribution of two Lyman-alpha photons emitted by an entangled pair of H(2p) atoms in the photodissociation of H2.

The angular distribution of two Lyman-alpha photons, i.e., the probability density that two Lyman-alpha photons are emitted in given directions, in the photodissociation of a hydrogen molecule have been measured at the hydrogen gas pressures of 0.40 and 0.13 Pa. We have found that the experimental angular distributions seem to approach the theoretical one by our group [J. Phys. B 40, 617 (2007)] with decreasing pressure, which indicates the generation of the entangled pair of H(2p) atoms shown in the theory and the role of the reaction of the entangled pair of H(2p) atoms with an H2 molecule that efficiently changes the entanglement.

Application of a simple asynchronous mechanical light chopper to multielectron coincidence spectroscopy.

A simple asynchronous mechanical light chopper, based on modification of a turbo-molecular pump, has been developed to extend the interval between light pulses in single bunch operation at the Photon Factory storage ring. A pulse repetition rate of 80 kHz was achieved using a cylinder rotating at 48000 rpm, with 100 slits of 80 microm width. This allows absolute timing of particles up to 12.48 micros instead of the single-bunch period of 624 ns. We have applied the chopper together with a light pulse monitor to measure multielectron coincidence spectra using a magnetic bottle time-of-flight electron spectrometer. With such a system, the electron energies are determined without any ambiguity, the folding of coincidence spectra disappears and the effect of false coincidences is drastically reduced.

Site-specific fragmentation caused by core-level photoionization in F(3)SiCH(2)CH(2)Si(CH(3))(3) vapor: comparison between Si:1s and 2p photoionizations by means of photoelectron-photoion-photoion triple-coincidence spectroscopy.

Site-specific fragmentation caused by Si:1s and 2p core-level photoionizations in F(3)SiCH(2)CH(2)Si(CH(3))(3) vapor was studied by energy-selected-photoelectron photoion-photoion triple-coincidence spectroscopy. The difference between the chemical shifts of the two Si sites is larger for the 1s ionization than for the 2p (2s) ionization. The fragmentation caused by the Si:1s ionization is more violent than that caused by the Si:2p ionization. The ions and ion pairs showing high site specificity for the Si:1s ionization belong to small fragments compared to those in the Si:2p ionization. Criteria for high site-specificity in fragmentation are discussed in conjunction with the present results.

Inner-shell excitation spectroscopy and fragmentation of small hydrogen-bonded clusters of formic acid after core excitations at the oxygen K edge.

Inner-shell excitation spectra and fragmentation of small clusters of formic acid have been studied in the oxygen K-edge region by time-of-flight fragment mass spectroscopy. In addition to several fragment cations smaller than the parent molecule, we have identified the production of HCOOH.H+ and H3O+ cations characteristic of proton transfer reactions within the clusters. Cluster-specific excitation spectra have been generated by monitoring the partial ion yields of the product cations. Resonance transitions of O1s(C[double bond]O/OH) electrons into pi(CO)* orbital in the preedge region were found to shift in energy upon clusterization. A blueshift of the O1s(C[double bond]O)-->pi(CO)* transition by approximately 0.2 eV and a redshift of the O1s(OH)-->pi(CO)* by approximately 0.6 eV were observed, indicative of strong hydrogen-bond formation within the clusters. The results have been compared with a recent theoretical calculation, which supports the conclusion that the formic-acid clusters consist of the most stable cyclic dimer andor trimer units. Specifically labeled formic acid-d, HCOOD, was also used to examine the core-excited fragmentation mechanisms. These deuterium-labeled experiments showed that HDO+ was formed via site-specific migration of a formyl hydrogen within an individual molecule, and that HD2O+ was produced via the subsequent transfer of a deuterium atom from the hydroxyl group of a nearest-neighbor molecule within a cationic cluster. Deuteron (proton) transfer from the hydroxyl site of a hydrogen-bond partner was also found to take place, producing deuteronated HCOOD.D+ (protonated HCOOH.H+) cations within the clusters.