Dissociation dynamics of fluorinated ethene cations:\ud from time bombs on a molecular level to double-regime dissociators\ud

The dissociative photoionization mechanism of internal energy selected C$_2$H$_3$F$^+$, 1,1-C$_2$H$_2$F$_2^+$, C$_2$HF$_3^+$ and C$_2$F$_4^+$ cations have been studied in the 13−20 eV photon energy range using imaging photoelectron photoion coincidence spectroscopy. Five predominant channels have been found; HF loss, statistical and non-statistical F loss, cleavage of the C–C bond post H or F-atom migration, and cleavage of the C=C bond. By modelling the breakdown diagrams and ion time-of-flight distributions using statistical theory, experimental 0 K appearance energies, E$_0$, of the daughter ions have been determined. Both C$_2$H$_3$F$^+$ and 1,1-C$_2$H$_2$F$_2^+$ are veritable time bombs with respect to dissociation via HF loss, where slow dissociation over a reverse barrier is followed by an explosion with large kinetic energy release. The first dissociative ionization pathway for C$_2$HF$_3$ and C$_2$F$_4$ involves an atom migration across the C=C bond, giving CF–CHF$_2^+$ and CF–CF$_3^+$, respectively, which then dissociate to form CHF$_2^+$ and CF$_3^+$. The nature of the F-loss pathway has been found to be bimodal for C$_2$H$_3$F and 1,1-C$_2$H$_2$F$_2$, switching from statistical to non-statistical behaviour as the photon energy increases. The dissociative ionization of C$_2$F$_4$ is found to be comprised of two regimes. At high internal energies, a long-lived excited electronic state is formed, which loses an F atom in a non-statistical process and undergoes statistical redistribution of energy among the nuclear degrees of freedom. This is followed by a subsequent dissociation. In other words only the ground electronic state phase space stays inaccessible. The accurate E$_0$ of CF$_3^+$ and CF$^+$ formation from C$_2$F$_4$ together with the now well established ∆$_f$Hº of C$_2$F$_4$ yield self-consistent enthalpies of formation for the CF$_3$, CF, CF$_3^+$, and CF$^+$ species

Context-dependent detection of fungal parasites in four ant species

The reaction between the allyl radical (C3H5˙) and acetylene (C2H2) in a heated microtubular reactor has been studied at the VUV beamline of the Swiss Light Source. The reaction products are sampled from the reactor and identified by their photoion mass-selected threshold photoelectron spectra (ms-TPES) by means of imaging photoelectron photoion coincidence spectroscopy. Cyclopentadiene is identified as the sole reaction product by comparison of the measured photoelectron spectrum with that of cyclopentadiene. With the help of quantum-chemical computations of the C5H7 potential energy surface, the C2H2 + C3H5˙ association reaction is confirmed to be the rate determining step, after which H-elimination to form C5H6 is prompt in the absence of re-thermalization at low pressures. The formation of cyclopentadiene as the sole product from the allyl + acetylene reaction offers a direct path to the formation of cyclic hydrocarbons under combustion relevant conditions. Subsequent reactions of cyclopentadiene may lead to the formation of the smallest polycyclic aromatic molecule, naphthalene

A Halomethane thermochemical network from iPEPICO experiments and quantum chemical calculations

Internal energy selected halomethane cations CH3Cl+, CH2Cl2+, CHCl3+, CH3F+, CH2F2+, CHClF2+ and CBrClF2+ were prepared by vacuum ultraviolet photoionization, and their lowest energy dissociation channel studied using imaging photoelectron photoion coincidence spectroscopy (iPEPICO). This channel involves hydrogen atom loss for CH3F+, CH2F2+ and CH3Cl+, chlorine atom loss for CH2Cl2+, CHCl3+ and CHClF2+, and bromine atom loss for CBrClF2+. Accurate 0 K appearance energies, in conjunction with ab initio isodesmic and halogen exchange reaction energies, establish a thermochemical network, which is optimized to update and confirm the enthalpies of formation of the sample molecules and their dissociative photoionization products. The ground electronic states of CHCl3+, CHClF2+ and CBrClF2+ do not confirm to the deep well assumption, and the experimental breakdown curve deviates from the deep well model at low energies. Breakdown curve analysis of such shallow well systems supplies a satisfactorily succinct route to the adiabatic ionization energy of the parent molecule, particularly if the threshold photoelectron spectrum is not resolved and a purely computational route is unfeasible. The ionization energies have been found to be 11.47 ± 0.01 eV, 12.30 ± 0.02 eV and 11.23 ± 0.03 eV for CHCl3, CHClF2 and CBrClF2, respectively. The updated 0 K enthalpies of formation, ∆fHo0K(g) for the ions CH2F+, CHF2+, CHCl2+, CCl3+, CCl2F+ and CClF2+ have been derived to be 844.4 ± 2.1, 601.6 ± 2.7, 890.3 ± 2.2, 849.8 ± 3.2, 701.2 ± 3.3 and 552.2 ± 3.4 kJ mol–1, respectively. The ∆fHo0K(g) values for the neutrals CCl4, CBrClF2, CClF3, CCl2F2 and CCl3F and have been determined to be –94.0 ± 3.2, –446.6 ± 2.7, –702.1 ± 3.5, –487.8 ± 3.4 and –285.2 ± 3.2 kJ mol–1, respectively

Playing stories?

Drawing on Janet Murray (1997), Katie Salen and Eric Zimmerman (2004), and other previous proposals, this article conceptualizes player agency as the possibility space for “meaningful” choice expressed via player action that translates into avatar action, afforded and constrained by a videogame’s design. It further distinguishes between four core dimensions of agency thus conceptualized: First, spatial-explorative agency is afforded by those elements of a videogame’s design that determine the player’s ability to navigate and traverse the game spaces via their avatar. Second, temporal-ergodic agency is afforded by those elements of a videogame’s design that determine the player’s options for interacting with the videogame as a temporal system. Third, configurative-constructive agency is afforded by those elements of a videogame’s design that allow the player to configure their avatar and/or (re)construct the game spaces. Fourth, narrative-dramatic agency is afforded by those elements of a videogame’s design that determine the player’s “meaningful” impact on the unfolding story. The article then moves on to analyze two case studies of independently developed videogames: ZA/UM’s role-playing game Disco Elysium (2019), whose complex nonlinear narrative structure primarily affords configurative and narrative agency, and System Era Softworks’s sandbox adventure game Astroneer (2019), whose procedurally generated game spaces and “open” game mechanics primarily afford explorative, constructive, and dramatic agency

Nitrogen matters: the difference between PANH and PAH formation

A solid understanding of and a reliable model for the formation pathways of polycyclic aromatic (nitrogen containing) hydrocarbons (PA(N)Hs) is needed to account for their abundance in the interstellar medium and in Titan's atmosphere as well as to mitigate the emission of these carcinogens in our terrestrial environment. We have investigated the phenyl + acrylonitrile reaction mechanism between 600 and 1200 K in a hot microreactor. Radical intermediates (C9H8N˙), formed by addition, and closed-shell C9H7N products, formed by subsequent hydrogen elimination, are isomer-selectively identified using photoion mass-selected threshold photoelectron spectroscopy in conjunction with Franck–Condon simulations. Although quinoline is the most stable product, the calculated potential energy surface and a kinetic model confirm that the reaction is kinetically controlled and yields four open-chain isomers instead. The absence of quinoline is in stark contrast with the isoelectronic phenyl + vinylacetylene reaction that produces naphthalene. Ab initio calculations suggest that this change is brought about by the stability of the nitrile group, which inhibits ring formation. Therefore, it is unlikely that nitrile precursors form nitrogen-containing rings, which calls for alternative pathways by which nitrogen atoms can be incorporated in aromatic systems to explain their presence in the ISM and Titan's atmosphereLaboratory astrophysics and astrochemistr

Whole-Genome Sequences and Classification of

In collaboration with the CDC’s Streptococcus Laboratory, we report here the whole-genome sequences of seven Streptococcus agalactiae bacteria isolated from laboratory-reared Long-Evans rats. Four of the S. agalactiae isolates were associated with morbidity accompanied by endocarditis, metritis, and fatal septicemia, providing an opportunity for comparative genomic analysis of this opportunistic pathogen.United States. National Institutes of Health (T32-OD010978)United States. National Institutes of Health (P30-ES002109

Chiral corrections to the SU(2)×SU(2)SU(2)\times SU(2) Gell-Mann-Oakes-Renner relation

The next to leading order chiral corrections to the $SU(2)\times SU(2)$ Gell-Mann-Oakes-Renner (GMOR) relation are obtained using the pseudoscalar correlator to five-loop order in perturbative QCD, together with new finite energy sum rules (FESR) incorporating polynomial, Legendre type, integration kernels. The purpose of these kernels is to suppress hadronic contributions in the region where they are least known. This reduces considerably the systematic uncertainties arising from the lack of direct experimental information on the hadronic resonance spectral function. Three different methods are used to compute the FESR contour integral in the complex energy (squared) s-plane, i.e. Fixed Order Perturbation Theory, Contour Improved Perturbation Theory, and a fixed renormalization scale scheme. We obtain for the corrections to the GMOR relation, $\delta_\pi$, the value $\delta_\pi = (6.2, \pm 1.6)$. This result is substantially more accurate than previous determinations based on QCD sum rules; it is also more reliable as it is basically free of systematic uncertainties. It implies a light quark condensate $\simeq \equiv |_{2\,\mathrm{GeV}} = (- 267 \pm 5 MeV)^3$. As a byproduct, the chiral perturbation theory (unphysical) low energy constant $H^r_2$ is predicted to be $H^r_2 (\nu_\chi = M_\rho) = - (5.1 \pm 1.8)\times 10^{-3}$, or $H^r_2 (\nu_\chi = M_\eta) = - (5.7 \pm 2.0)\times 10^{-3}$.Comment: A comment about the value of the strong coupling has been added at the end of Section 4. No change in results or conslusion