Auger decay and subsequent fragmentation pathways of ethylene following K-shell ionization

Citation: Gaire, B., Haxton, D. J., Sturm, F. P., Williams, J., Gatton, A., Bocharova, I., . . . Weber, T. (2015). Auger decay and subsequent fragmentation pathways of ethylene following K-shell ionization. Physical Review A, 92(1), 13. doi:10.1103/PhysRevA.92.013408The fragmentation pathways and dynamics of ethylene molecules after core ionization are explored using coincident measurements of the Auger electron and fragment ions by employing the cold target recoil-ion momentum spectroscopy method. The influence of several factors on the dynamics and kinematics of the dissociation is studied. These include propensity rules, ionization mechanisms, symmetry of the orbitals from which the Auger electrons originate, multiple scattering, conical intersections, interference, and possible core-hole localization for the double ionization of this polyatomic molecule. Energy correlation maps allow probing the multidimensional potential energy surfaces and, in combination with our multiconfiguration self-consistent field calculations, identifying the populated electronic states of the dissociating dication. The measured angular distributions of the Auger electrons in the molecular frame further support and augment these assignments. The deprotonation and molecular hydrogen ion elimination channels show a nearly isotropic Auger electron angular distribution with a small elongation along the direction perpendicular to the molecular axis. For the symmetric breakup the angular distributions show a clear influence of multiple scattering on the outgoing electrons. The lowest kinetic energy release feature of the symmetric breakup channel displays a fingerprint of entangled Auger and photoelectron motion in the angular emission pattern identifying this transition as an excellent candidate to probe core-hole localization at a conical intersection of a polyatomic molecule.Additional Authors: Landers, A. L.;Belkacem, A.;Dorner, R.;Weber, T

Robot education peers in a situated primary school study: personalisation promotes child learning

The benefit of social robots to support child learning in an educational context over an extended period of time is evaluated. Specifically, the effect of personalisation and adaptation of robot social behaviour is assessed. Two autonomous robots were embedded within two matched classrooms of a primary school for a continuous two week period without experimenter supervision to act as learning companions for the children for familiar and novel subjects. Results suggest that while children in both personalised and non-personalised conditions learned, there was increased child learning of a novel subject exhibited when interacting with a robot that personalised its behaviours, with indications that this benefit extended to other class-based performance. Additional evidence was obtained suggesting that there is increased acceptance of the personalised robot peer over a non-personalised version. These results provide the first evidence in support of peer-robot behavioural personalisation having a positive influence on learning when embedded in a learning environment for an extended period of time

Computational approaches for modeling human intestinal absorption and permeability

Human intestinal absorption (HIA) is an important roadblock in the formulation of new drug substances. Computational models are needed for the rapid estimation of this property. The measurements are determined via in vivo experiments or in vitro permeability studies. We present several computational models that are able to predict the absorption of drugs by the human intestine and the permeability through human Caco-2 cells. The training and prediction sets were derived from literature sources and carefully examined to eliminate compounds that are actively transported. We compare our results to models derived by other methods and find that the statistical quality is similar. We believe that models derived from both sources of experimental data would provide greater consistency in predictions. The performance of several QSPR models that we investigated to predict outside the training set for either experimental property clearly indicates that caution should be exercised while applying any of the models for quantitative predictions. However, we are able to show that the qualitative predictions can be obtained with close to a 70% success rate

Weak dorsolateral prefrontal response to social criticism predicts worsened mood and symptoms following social conflict in people at familial risk for schizophrenia

Understanding the specific mechanisms that explain why people who have relatives with schizophrenia (i.e., people at familial high risk; FHR) are more likely to develop the disorder is crucial for prevention. We investigated a diathesis-stress model of familial risk by testing whether FHR individuals under-recruit brain regions central to emotion regulation when exposed to social conflict, resulting in worse mood and symptoms following conflict. FHR and non-FHR participants listened to critical, neutral, and praising comments in an fMRI scanner before completing 4 weeks of daily-diary records. Compared to non-FHR individuals, FHR individuals under-recruited the bilateral dorsolateral prefrontal cortex (DLPFC)—a region strongly implicated in cognitive emotion regulation—following criticism. Furthermore, within FHR participants, weak DLPFC response to criticism in the laboratory task was associated with elevated negative mood and positive symptoms on days with distressing social conflicts in daily-diary assessments. Results extend diathesis-stress models of schizophrenia by clarifying neural and environmental pathways to dysregulation in FHR individuals

Photo-double-ionization of ethylene and acetylene near threshold

We present kinematically complete measurements of the photo-double-ionization of ethylene (double CC bond) and acetylene (triple CC bond) hydrocarbons just above the double-ionization threshold. We discuss the results in terms of the coincident kinetic energy of the photoelectrons and the nuclear kinetic-energy release of the recoiling ions. We have incorporated quantum chemistry calculations to interpret which of the electronic states of the dication have been populated and trace the various subsequent fragmentation channels. We suggest pathways that involve the electronic ground and excited states of the precursor ethylene dication and explore the strong influence of the conical intersections between the different electronic states. The nondissociative ionization yield is small in ethylene and high in acetylene when compared with the dissociative ionization channels. The reason for such a striking difference is explained in part on the basis of a propensity rule that influences the population of states in the photo-double-ionization of a centrosymmetric closed-shell molecule by favoring singlet ungerade and triplet gerade final states. This propensity rule and the calculated potential-energy surfaces clarify a picture of the dynamics leading to the observed dication dissociation products

Molecular frame photoelectron angular distributions for core ionization of ethane, carbon tetrafluoride and 1,1-difluoroethylene

Molecular frame photoelectron angular distributions (MFPADs) are measured in electron-ion momentum imaging experiments and compared with complex Kohn variational calculations for carbon K-shell ionization of carbon tetrafluoride (CF4), ethane (C2H6) and 1,1-difluoroethylene (C2H2F2). While in ethane the polarization averaged MFPADs show a tendency at low energies for the photoelectron to be emitted in the directions of the bonds, the opposite effect is seen in CF4. A combination of these behaviors is seen in difluoroethylene where ionization from the two carbons can be distinguished experimentally because of their different K-shell ionization potentials. Excellent agreement is found between experiment and simple static-exchange or coupled two-channel theoretical calculations. However, simple electrostatics do not provide an adequate explanation of the suggestively simple angular distributions at low electron ejection energies

Molecular frame photoelectron angular distributions for core ionization of ethane, carbon tetrafluoride and 1,1-difluoroethylene

Molecular frame photoelectron angular distributions (MFPADs) are measured in electron-ion momentum imaging experiments and compared with complex Kohn variational calculations for carbon K-shell ionization of carbon tetrafluoride (CF4), ethane (C2H6) and 1,1-difluoroethylene (C2H2F2). While in ethane the polarization averaged MFPADs show a tendency at low energies for the photoelectron to be emitted in the directions of the bonds, the opposite effect is seen in CF4. A combination of these behaviors is seen in difluoroethylene where ionization from the two carbons can be distinguished experimentally because of their different K-shell ionization potentials. Excellent agreement is found between experiment and simple static-exchange or coupled two-channel theoretical calculations. However, simple electrostatics do not provide an adequate explanation of the suggestively simple angular distributions at low electron ejection energies