Cluster emission and chemical reactions in oxygen and nitrogen ices induced by fast heavy-ion impact.

Two ices, O2 and a mixture of O2 and N2, are bombarded by 252Cf fission fragments (FF) (approximately 65 MeV at target surface); the emitted positive and negative secondary ions are analyzed by time-of-flight mass spectrometry (TOF-SIMS). These studies shall enlighten sputtering from planetary and interstellar ices. Three temperature regions in the 28-42-K range are analyzed: (1) before N2 sublimation, in which hybrid chemical species are formed, (2) before O2 sublimation, in which the TOF mass spectrum is dominated by low-mass (O2)p cluster ions and (3) after O2 sublimation, in which (N2)p or (O2)p cluster ions are practically inexistent. In the first region, four hybrid ion series are observed: NOn-1+, N2On-2(+/-), and N4On-4(-). In the second region, two positive and negative ion series are identified: (O2)pO(+/-) and (O2)pO2(+/-). Their yield distributions are fitted by the sum of two decreasing exponentials, whose decay constants are the same for all series. It is observed that the cluster ion desorption from solid oxygen is very similar to that of other frozen gases, but its yield distribution oscillates with a three- or six-atom periodicity, suggesting O3 or 3O2 units in the cluster structure, respectively.

A synchrotron beamline for delivering high purity vacuum ultraviolet photons.

We report on the current status and performance of the toroidal grating monochromator beamline at the Brazilian Synchrotron Light Laboratory (Laboratorio Nacional de Luz Sincrotron). This beamline provides photons in the vacuum ultraviolet and soft x-ray regions from 12 to 330 eV with three interchangeable gratings. We report on the improvement, which allows the possibility of choosing the light polarization degree from linear to almost circular. Here, we also describe the development of a new apparatus, namely, the mirror-inserted harmonic attenuator and calibrating-device with a long length (MIRHACLLE). All beamlines based on diffraction gratings suffer from the problem of high harmonics contaminations to some extent. The MIRHACLLE provides a way to efficiently suppress high harmonics from 25% to 1 ppm in a grazing incidence bending magnet beamline. Its principle of operation relays on the absorption of the high energy photons in a gas phase region. It allows negligible high harmonics contamination for photon energies ranging from 12 eV to the gas first ionization threshold, 21.6 eV, in the case of neon. We also demonstrate the possibility to use this device for energy calibration and resolution evaluation together with any experiment needing its filtering capabilities. The device is also very cost effective compared to other filters presented previously in the literature.

H2S ultrafast dissociation probed by energy-selected resonant Auger electron-ion coincidence measurements.

We have studied the ultrafast dissociation of the H2S molecule upon S 2p3/2-->6a1 inner-shell excitation by combining high-resolution resonant Auger spectroscopy and energy-selected Auger electron-ion coincidence measurements. Auger final states have been correlated to the different fragmentation pathways (S+, HS+, and H2S+ ions). As an original result, we evidence a three-step mechanism to describe the resonant production of S+: the Auger recombination in the HS* fragment is followed for the A 3Pi and c 1Pi states by the S++H fragmentation mechanism.

Threshold photoelectron spectroscopy of ozone.

Threshold photoelectron spectrum of ozone is presented for the first time at a resolution of 21-38 meV using synchrotron radiation in the energy region of 12-21 eV. The ionization energies of the first ionized states were determined and an interpretation of the O3 spectrum with respect to its first three ionic states, 1 2A1, 1 2B2, and 1 2A2, is presented. Above 16 eV the enhancement of the intensities of the 2 2B1, 3 2A1, and 4 2B2 band systems due to the contribution of indirect processes was observed, not accessible by conventional photoelectron spectroscopy. It was also resolved and assigned the extensive vibrational structures of ozone. Between 15.5 and 18.5 eV the main band contours are similar to those found in conventional photoelectron spectroscopy, except that our threshold photoelectron spectrum reveals extensive additional vibrational structures. The band 2 2B1 was found to present an irregular vibrational spacing DeltaE, with a minimum value of 80 meV at approximately 16.47 eV.

Electronic sputtering produced by fission fragments on condensed CO and CO2.

Condensed CO and CO2 are bombarded by approximately 65 MeV 252Cf fission fragments and the desorbed ions are analyzed by time-of-flight mass spectrometry as a function of target temperature, in the ranges 25-33 K and 75-91 K, respectively. Absolute desorption yields are measured up to complete ice sublimation. The mass spectra of both ice targets reveal the emission of: (1) low mass ions, produced by direct Coulomb interaction of the highly charged projectiles and delta-electrons with CO and CO2, and (2) pronounced series of cluster ions. The basic ice cluster structures (CO)n and (CO2)n are present in the emitted cluster series such as (CO)nCO+, (CO2)nCO2+, or (CO2)nCO3-. In the case of CO ice, however, the intense production of the series Cn+, Cn-, and (CO)mCn+ shows that Cn is the main cluster structure, consequence of a higher concentration of free carbon atoms in the nuclear track plasma of CO ice than in that of CO2 ice. Ion cluster abundance is observed to decrease exponentially with cluster mass. The decay constant is k(n) congruent with 0.13, about the same for series based on (CO)n and (CO2)n, but a factor 3.3 higher for the Cn series. The Cn clusters are formed by gas-phase condensation, but the (CO)n and (CO2)n clusters are produced by fracturing of the highly excited solid around the nuclear track. A dramatic reduction of the ion desorption yield is observed near T = 29 K for CO and near T = 85 K for CO2, when fast sublimation occurs and ice thickness vanishes. Close to sublimation temperature, the decay constant of the (CO)2Cn+ series increases due to a decreasing formation probability of large Cn clusters.

The electronic structure of free water clusters probed by Auger electron spectroscopy.

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

Core excitation in O3 localized to one of two symmetry-equivalent chemical bonds: molecular alignment through vibronic coupling.

Core excitation from terminal oxygen OT in O3 is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger-Doppler effect which is observable when O3 is core excited to the highly dissociative OT1s(-1)7a1 1 state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic-field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one bond, not on the total molecular orientation. The localization of the valence orbital "7a1" is caused by mixing of the valence orbital "5b2" through vibronic coupling of antisymmetric stretching mode with b2 symmetry. To the best of our knowledge, it is the first discussion of the localization of a core excitation of O3. This result explains the success of the widely used assumption of localized core excitation in adsorbates and large molecules.

Relativistic and interchannel coupling effects in photoionization angular distributions by synchrotron spectrocopy of laser cooled atoms.

We investigate the angular distribution of photoionization fragments at low photon energies (12-40 eV) in an open shell atom, by synchrotron radiation recoil ion momentum spectroscopy in a laser cooled and trapped sample. For cesium atoms, for which relativistic effects play an important role and the ion recoil is relatively small, we could determine large and rapid changes of the asymmetry parameter beta from two, observed for s electrons outside resonances and far from the Cooper minimum. They can be explained by relativistic effects and interchannel coupling arising from final state configuration mixing.

Interference quenching of nu(")=1 vibrational line in resonant photoemission of N2: a possibility to obtain geometrical information on the core-excited state.

An interference quenching of the nu(")=1 vibrational line in the resonant Auger decay of N 1s-->pi(*) core-excited N2 is observed and analyzed. The intensity ratio between the nu(")=1 and nu(")=0 vibrational levels of the X2Sigma(+)(g) final state shows a surprising nonmonotonous variation as a function of frequency detuning, going through a minimum with a complete suppression of nu(")=1. We have developed a simple model which shows a linear relation between the value of the detuning frequency for this minimum and the equilibrium bond distance R(0)(c) of the core-excited state. A new way is thus established of determining the equilibrium bond distance for the core-excited state with a precision deltaR(0)(c)<10(-3) A.

Observation of a continuum-continuum interference hole in ultrafast dissociating core-excited molecules.

The femtosecond dissociation of HCl after core excitation has been studied through the resonant Auger decay. The spectra contain contributions from decay occurring at both "molecular" and "atomic" internuclear distances. We have observed a new interference mechanism in these spectra: An atomic spectral line develops into a negative spectral contribution, a "hole," when detuning the excitation energy from the maximum of the Cl2p(-1)sigma(*) resonance. Resonant x-ray scattering theory quantitatively explains this behavior as due to a novel destructive continuum-continuum interference between molecular and atomic contributions to the Auger decay.