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

Efficient neutralization of core ionized species in an aqueous environment

Abstract Core ionization dynamics of argon–water heteroclusters ArM[H₂O]N are investigated using a site and process selective experimental scheme combining 3 keV electron irradiation with Auger electron–ion–ion multi-coincidence detection. The formation of Ar 2p⁻¹ vacancies followed by non-radiative decay to intermediate one-site doubly ionized states Ar²⁺(3p⁻²)−ArM−1[H₂O]N and subsequent redistribution of charge to the cluster environment are monitored. At low argon concentrations the emission of an [H₂O]n′H⁺/[H₂O]n′′H⁺ ion pair is the dominant outcome, implying on high efficiency of charge transfer to the water network. Increasing the condensation fraction of argon in the mixed clusters and/or to pure argon clusters is reflected as a growing yield of Arm′+/Arm′′+ ion pairs, providing a fingerprint of the precursor heterocluster beam composition. The coincident Auger electron spectra, resolved with better than 1 eV resolution, show only subtle differences and thereby reflect the local nature of the initial Auger decay step. The results lead to better understanding of inner shell ionization processes in heterogeneous clusters and in aqueous environments in general

15th international conference on electronic spectroscopy and structure:book of abstracts

Welcome to ICESS 15th Welcome to the 15th ICESS conference! Finally, after five years of waiting it is our pleasure to welcome you - the whole international community – to Oulu, Finland. The scientific program built in collaboration with international advisory board (IAB) covers widely the areas of research and surely engages plenty of discussions and ideas for future collaborations. Great thanks for participating and making the event possible! Let us all make the event pleasant respecting the diversity and committing to strengthening the international community of ICESS. Welcome to Oulu! ICESS local committee: Marko Huttula, chair Minna Patanen, program committee Samuli Urpelainen, Satu Ojala, local organizatio

Disentangling Auger decays in O₂ by photoelectron-ion coincidences

Abstract In non-resonant Auger electron spectroscopies, multi core-ionized states lead to numerous energetically close-lying electronic transitions in Auger spectra, this hampering the assignment and interpretation of the experimental results. Here we reveal a new method to overcome this intrinsic limitation of non-resonant inner-shell spectroscopies. In a proof-of-principle experiment performed for the O₂ molecule, most of the Auger final states are dissociative, and we measure in coincidence the kinetic energy of the photoelectron and the kinetic energy release of the (O⁺, O⁺) ion pairs produced after the Auger decay of the O 1s−1 core-ionized states. The Auger final states are assigned using energy conservation. We fully separate the contributions from the ⁴Σ− and ²Σ− intermediate ionic states and conclusively demonstrate that the Auger decay probability can dramatically depend on the different O₂ 1s−1 intermediate multiplet states. In addition, a metastable Auger final state also exists, with lifetime longer than 3.8 μs, and clear changes are observed in both branching ratio and spectral profile of the O 1s photoelectron spectrum when they are recorded in coincidence with either O₂⁺⁺ or with other ionic species. These changes are attributed to the population of the metastable B′³Σ−u(ν′′=0) Auger final state via different intermediate states

Influence of organic acids on the surface composition of sea spray aerosol

Abstract Recent studies on sea spray aerosol indicate an enrichment of Ca2+ in small particles, which are often thought to originate from the very surface of a water body when bubbles burst. One model to explain this observation is the formation of ion pairs between Ca2+(aq) and surface-active organic species. In this study, we have used X-ray photoelectron spectroscopy to probe aqueous salt solutions and artificial sea spray aerosol to study whether ion pairing in the liquid environment also affects the surface composition of dry aerosol. Carboxylic acids were added to the sample solutions to mimic some of the organic compounds present in natural seawater. Our results show that the formation of a core–shell structure governs the surface composition of the aerosol. The core–shell structure contrasts previous observations of the dry sea spray aerosol on substrates. As such, this may indicate that substrates can impact the morphology of the dried aerosol

Solvent and cosolute dependence of Mg surface enrichment in submicron aerosol particles

Abstract The formation of multicomponent aerosol particles from precursor solution droplets often involves segregation and surface enrichment of the different solutes, resulting in non-homogeneous particle structures and diverse morphologies. In particular, these effects can have a significant influence on the chemical composition of the particle–vapor interface. In this work, we investigate the bulk/surface partitioning of inorganic ions, Na⁺, Mg² ⁺, Ca² ⁺, Cl⁻ and Br⁻, in atomiser-generated submicron aerosols using synchrotron radiation based X-ray photoelectron spectroscopy (XPS). Specifically, the chemical compositions of the outermost few nm thick surface layers of non-supported MgCl₂/CaCl₂ and NaBr/MgBr₂ particles are determined. It is found that in MgCl₂/CaCl₂ particles, the relative abundance of the two species in the particle surface correlates well with their mixing ratio in the parent aqueous solution. In stark contrast, extreme surface enrichment of Mg² ⁺ is observed in NaBr/MgBr₂ particles formed from both aqueous and organic solution droplets, indicative of core–shell structures. Structural properties and hydration state of the particles are discussed

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

Abstract Vibrational state-resolved photoelectron anisotropy parameters, β, for the ˜X2B1, ˜B2B2, and ˜C2B1 state ionizations of bromobenzene have been recorded at photon energies ranging from 20.5 to 94 eV, thus spanning the region of the expected bromine Cooper minimum (CM). The ˜X state displays no CM and its β value is also independent of vibrational level, in accord with the Franck-Condon approximation. The ˜B and ˜C state β values display the CM to differing degrees, but both show a vibrational dependence that extends to energies well below the obvious CM dip. Calculations are presented that replicate these observations. We thus demonstrate a wide-ranging Franck-Condon approximation breakdown detected in the β 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, quasilinear variations across the studied range of photon energy, but with no apparent correlation with the CM position

Electron–ion coincidence spectroscopy of a large organic molecule:photofragmentation of avobenzone after valence and core ionisation

Abstract The Avobenzone (AVOB) molecule is very photoactive and undergoes irreversible degradation upon irradiation. We studied its valence and core-level (C1s and O1s) photoionisation and subsequent photofragmentation with photoelectron spectroscopy and photoelectron–photoion–photoion coincidence (PEPIPICO) spectroscopy. AVOB is one of the largest molecules studied with this technique. The results show that the AVOB molecule dissociates into an extensive range of fragments by different pathways with little element or site-selectivity. The coincident maps were used to determine selected fragment separation sequences by analysing the slopes of patterns from ion pairs after the core ionisation. Charge delocalisation over the benzene rings and their relative stability favor fragmentation by cleavage of the bridge between them

Surface analysis of tissue paper using laser scanning confocal microscopy and micro-computed topography

Abstract Tissue paper softness relies on two major factors, the bulk softness, which can be indicated by the elasticity of the sheet, and surface softness. Measurement of surface softness is complicated and often requires a multi-step process. A key parameter defining surface softness is the topography of the surface, particularly the crepe structure and its periodicity. Herein, we present a novel approach to measure and quantify the tissue paper surface crepe structure and periodicity based on the detection of waviness along the sample using laser scanning confocal microscopy (LSM) and X-ray tomography (XRT). In addition, field emission scanning electron microscope (FESEM) was used to characterize the tissue paper surface. We demonstrate that surface topography is directly correlated to the erosion of the doctor blade, which is used to remove the dry tissue paper from the Yankee cylinder. Because of its accuracy and simplicity, the laser confocal microscopy method has the potential to be used directly on the production line to monitor the production process of the tissue paper. XRT revealed more structural details of the tissue paper structure in 3D, and it allowed for the reconstruction of the surface and the internal structure of the tissue paper

Hybrid films of cellulose nanofibrils, chitosan and nanosilica:structural, thermal, optical, and mechanical properties

Abstract Organic-inorganic hybrid films were fabricated from cellulose nanofibrils (CNF) and nanosilica (5–30% wt) embedded in a chitosan (Chi) biopolymer matrix using a slow evaporation method. The self-standing films exhibited high strength and modulus up to 120 ± 5 MPa and 7.5 ± 0.4 GPa, respectively, which are remarkably high values for biopolymer/chitosan hybrids. Scanning electron microscopy showed that the nanosilica is formed of larger aggregates within the lamellar CNF network structure. This observation was further confirmed using synchrotron-based scanning transmission x-ray microscopy (STXM) with the capability to determine the spatial and chemical distribution analysis of the constituents of films. It is interesting that the thermal stability of the hybrid films improved as the nanosilica content increased. Furthermore, the nanosilica effectively filled the pores in the CNF network, thus decreasing the UV transmission and the visible light transmittance of the films