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Abstract The resonance-stabilization of the propargyl radical (C3H3) makes it among the most important reactive intermediates in extreme environments and grants it a long enough lifetime to recombine in both terrestrial combustion media and cold molecular clouds in space. This makes the propargyl self-reaction a pivotal step in the formation of benzene, the first aromatic ring, to eventually lead to polycyclic aromatic hydrocarbons in a variety of environments. In this work, by producing propargyl radicals in a flow tube where propyne reacted with F atoms and probing the reaction products by mass-selected threshold-photoelectron spectroscopy (TPES), we identified eight C6H6 products in total, including benzene. On top of providing the first comprehensive measurements of the branching ratios of the eight identified C6H6 isomers in the propargyl self reaction products (4 mbar, 298 K conditions), this study also highlights the advantages and disadvantages of using isomer-selective TPES to identify and quantify reaction products.

Abstract Polycyclic aromatic hydrocarbons (PAHs) are widely established as ubiquitous in the interstellar medium (ISM), but considering their prevalence in harsh vacuum environments, the role of ionisation in the formation of PAH clusters is poorly understood, particularly if a chirality-dependent aggregation route is considered. Here we report on photoelectron spectroscopy experiments on [4]helicene clusters performed with a vacuum ultraviolet synchrotron beamline. Aggregates (up to the heptamer) of [4]helicene, the smallest PAH with helical chirality, were produced and investigated with a combined experimental and theoretical approach using several state-of-the-art quantum-chemical methodologies. The ionisation onsets are extracted for each cluster size from the mass-selected photoelectron spectra and compared with calculations of vertical ionisation energies. We explore the complex aggregation topologies emerging from the multitude of isomers formed through clustering of P and M, the two enantiomers of [4]helicene. The very satisfactory benchmarking between experimental ionisation onsets vs. predicted ionisation energies allows the identification of theoretically predicted potential aggregation motifs and corresponding energetic ordering of chiral clusters. Our structural models suggest that a homochiral aggregation route is energetically favoured over heterochiral arrangements with increasing cluster size, hinting at potential symmetry breaking in PAH cluster formation at the scale of small grains.

Abstract An achiral chromophore can acquire a chiral spectroscopic signature when interacting with a chiral environment. This so-called induced chirality is documented in electronic or vibrational circular dichroism, which arises from the coupling between electric and magnetic transition dipoles. Here, we demonstrate that a chiroptical response is also induced within the electric dipole approximation by observing the asymmetric scattering of a photoelectron ejected from an achiral chromophore in interaction with a chiral host. In a phenol–methyloxirane complex, removing an electron from an achiral aromatic π orbital localised on the phenol moiety results in an intense and opposite photoelectron circular dichroism (PECD) for the two enantiomeric complexes with (R) and (S) methyloxirane, evidencing the long-range effect (~5 Å) of the scattering chiral potential. This induced chirality has important structural and analytical implications, discussed here in the context of growing interest in laser-based PECD, for in situ, real time enantiomer determination.

This study presents the method of fixed-photon-energy double-imaging photoelectron photoion coincidence (i2PEPICO) utilized to investigate the dissociation of state-selected ions. Vacuum ultraviolet (VUV) synchrotron radiation at one fixed photon energy of hν = 21.2 eV, the He(I) atomic resonance energy, is employed as a light source to ionize molecules. Various dynamic information including time-of-flight (TOF) mass spectra, mass-selected photoelectron spectra (PES), and electron and ion kinetic energy correlation diagrams corresponding to each mass are obtained efficiently with the multiplexed capabilities of i2PEPICO, thereby revealing the detailed dissociation mechanisms of ions. As representative examples, dissociation of state-selected O2+ ions prepared in the b4∑g− and B2∑g− electronic states and CH3F+ ions in the X2E, A2A1, and B2E states were selected and investigated.

We investigate the vacuum ultraviolet (VUV) photodynamics of gas phase 1- and 2-cyanonaphthalene and cyanobenzene, recently detected in the Taurus molecular cloud, by combining synchrotron radiation and a double imaging electron/ion coincidence setup. The high-resolution threshold photoelectron spectra (TPES) of all three molecules are obtained experimentally from which the adiabatic ionization energies are reported with very high accuracy, particularly for 2-cyanonaphthalene, for which no data exist at this level of precision. Theoretical calculations are performed to compare with the TPES for the ground electronic state of the cations. Furthermore, the different features observed in the extended TPES have been assigned to the different molecular orbitals with the help of the outer valence Green's function calculations. The present experiments also shed light on the kinetic energy distribution of the photoelectrons as a function of the incident photon energy, to describe their contribution to the photoelectric heating effect in the interstellar medium. In this context, we show how kinetic energy distributions can be obtained from our data for any given photon energy, such as the omnipresent Ly α line, or any given interstellar radiation field (ISRF). In addition, from the total ion yields, we estimate the photorates for a few ISRFs. Finally, we discuss the photodissociation of the two cyanonaphthalenes, quoting the activation energies of the dissociation channels with the help of Rice–Ramsperger–Kassel–Marcus modeling. It is observed that CN substitution does not cause any appreciable change to the VUV dissociative photoionization relaxation channel.

Proline plays an important role in determining the structures of proteins and peptides, but the conformer landscape of proline is still not fully mapped. Here, the authors show the conformer-specific cation fragmentation and photoelectron circular dichroism of proline during its vacuum ultraviolet photoionization.

Photoelectron/photoion imaging spectrometry employing dispersed VUV radiation from the SOLEIL synchrotron has been used to study the predissociation of N2+ states located up to 1.3 eV above the ion's first dissociation limit. Branching ratios for unimolecular decay into either N2+ or N+ were obtained by measuring coincidences between threshold electrons and mass-selected product ions, using a supersonic beam of either 14N2 or 15N2 as photoionization target. The results confirm that predissociation of the C2Σu+ state of 14N2+ is faster than emission to the electronic ground-state by a factor 10 or more for all vibrational levels v′ ≥ 3, while for 15N2+ the two decay modes have comparable probabilities for the levels v′ = 3, 4, and 5. In contrast, no significant isotope effect could be observed for the other states of N2+ identified in the photoelectron spectrum. For both 14N2+ and 15N2+ isotopologues all vibrational levels of these other states decay to an extent of at least 95% by predissociation.

The dropout rate is the most significant disadvantage in Massive Open Online Courses (MOOC); most of the time, it exceeds 90%. This research compares the effect of cognitive bias, gamification, monetary compensation, and student characteristics (gender, age, years of education, student geographical location, and interest in the course certificate) on dropout. We use survival analysis to identify the predictors of dropout and its related factors. The results showed the lowest dropout (74.2%) for cognitive bias and gamification. The results showed that the Peanut effect bias favors the lowest risk of drop up. Likewise, the findings showed the interest in the final certificate as a predictor of retention to complete a four-week MOOC.

Photoelectron circular dichroism (PECD) is an intense orbital-specific chiroptical effect observed as asymmetries in the angular distribution of photoelectrons produced by photoionization of randomly oriented pure enantiomers with circularly polarized light. After a broad introduction placing this effect in the context of new physical chiral-sensitive methods, we review the main characteristics of PECD in terms of molecular photoionization dynamics. We stress also the analytical capabilities of PECD to retrieve enantiomeric excesses (e.es.) and to probe subtle details of the whole molecular potential, some of them exemplified by the showcase camphor and fenchone molecules. We then present the case of the amino acid alanine for which an interplay between PECD and conformer population is rationalized. Based on this study, we propose a photophysical astrophysical scenario for the origin of life’s homochirality, relying upon the asymmetry of the associated recoiling alanine parent ion that could lead at the relevant Lyman-α energy to an e.e. of up to 4% in a given line of sight, which appears independent of the temperature. In an attempt to generalize this scenario to other amino acids, new data on proline showing an e.e. of 12%, of the same sign as alanine, are also presented. Abbreviations ARPES: Angle-resolved photoemission; CMS-Xa: Continuum multiple scattering with Xa local-exchange potential; CPL: Circularly polarized light; CD: Circular dichroism; CSM: Circumstellar medium; DPI: Dissociative ionization; HHG: High harmonics generation; HOMO: Highest occupied molecular orbital; ISM: Interstellar medium; KE: Kinetic energy; MS: Mass spectrometry; MW: Microwave; PAD: Photoelectron angular distribution; PECD: Photoelectron circular dichroism; PECD-PICO: Photoelectron circular dichroism / photoion coincidence; PEPICO: Photoelectron / photoion coincidence; PES: Photoelectron spectrum; PV: Parity Violation; REMPI: Resonance-enhanced multi-photon ionization; RH: Resistive heating; TD: Thermodesorption; UV: Ultra-violet; VMI: Velocity map imaging; VUV: Vacuum ultra-violet.

While Common Pool Resource (CPR) theory has been widely applied to forestry, there are few examples of using the theory to study large-scale governance. In this paper we test the applicability of CPR theory to understanding forest governance and outcomes in Indonesia between 1965 and 2012. Indonesia contains one of the world’s largest tropical forests, and experienced rapid deforestation during this time frame, with forest cover dropping from close to 85% to less than 50%. Using a mixture of within case comparison and process tracing methods, we identify key variables that influenced the levels of deforestation during two time periods: before 1998, when governance was dominated by the dictatorship of President Suharto, and after 1998, when democratic governance and political decentralization were initiated, and deforestation rates fell and then rose again. Our results point to the value of CPR theory in identifying important variables that influence sustainability at large scales, however they also illustrate important limitations of CPR theory for the study of forests with large spatial extent and large numbers of users. The presence and absence of key variables from CPR theory did emerge as important causes of deforestation. However, some variables, such as strong leadership and local rule-making, appeared to work in the opposite direction as predicted by CPR theory. In addition, key variables that may have influenced deforestation rates are not well captured in CPR theory. These include the intention of the governance system, the presence of clientelistic politics, the influences of international politics and markets, and the influence of top-down governance. Given that CPR theory does not fully explain the case at hand, its applicability, as is, to large-scale commons should be treated with some caution.

The most significant disadvantage in the use of MOOCs is their high drop out rates, which reaches between 88.3% and 90%. This research examined the desertion from 15 MOOCs, the following factors and their relation to desertion were assessed, characteristics of the students (gender, language, educational level, age, interest in the final certificate) and aspects of the courses (data lost at the time of registration, duration of the MOOC, course discipline, number of total questions and by evaluation). The results, based on survival analysis, indicate the probability of desertion is the highest on the first and last weeks of the MOOC. Our findings show that the probability of dropout is affected by the number of questions in each evaluation, the educational level of the participants, their age and their interest in the certificate. Missing data in the registration form was found to be associated with desertion being a significant pre-dictor of risk of quitting. Finally, the lack of interest in the certificate was found to be a predictor of the highest risk of dropping out. Possible strategies to reduce the desertion behavior at MOOCs are discussed.

We develop an analytic framework for the analysis of robustness in social-ecological systems (SESs) over time. We argue that social robustness is affected by the disturbances that communities face and the way they respond to them. Using Ostrom's ontological framework for SESs, we classify the major factors influencing the disturbances and responses faced by five Indiana intentional communities over a 15-year time frame. Our empirical results indicate that operational and collective-choice rules, leadership and entrepreneurship, monitoring and sanctioning, economic values, number of users, and norms/social capital are key variables that need to be at the core of future theoretical work on robustness of self-organized systems.