ALBERT

Notes: This paper reports three independent studies. In the first study, the infrared band shapes and relative intensities of gaseous thiirane-d4 (ethylene sulfide-d4, C2D4S), the Raman spectrum of liquid thiirane-d4, and infrared spectra of gaseous cis- and trans-1, 2-dideuteriothiirane, (CHD)2S, are reported for the first time. The vibrational spectra of C2H4S, C2D4S, and some bands of cis-(CHD)2S are assigned from the symmetry analysis, group frequencies, infrared band shapes, and Raman polarization data. The frequencies so assigned are used to derive a modified valence force field, (MVFF), which reproduces them well, allows the remaining fundamental frequencies of cis-(CHD)2S to be found, and allows the spectrum of trans-(CHD)2S to be assigned. The MVFF is then further refined to optimize the fit to the 46 assigned frequencies of the four molecules. Twenty four nonzero force constants fit the 46 frequencies with an average error of 0.4%. The assignment is thus well based and self-consistent. Inthe second study, ab initio SCF calculations of optimum geometry, vibrational frequencies, and IR intensities of thiirane, thiirene, and a number of isotopically substituted derivatives are reported for the 6-31G*, 3-21G, and STO 3G bases. The force constants of thiirane from the 6-31G* basis are in good agreement with those of the MVFF when allowance is made for the fact that some were constrained to zero in the MVFF. The potential energy distributions from the ab initio and normal coordinate calculations agree well, with the former confirming some defects in the latter. The 6-31G* force constants multiplied by 0.80 reproduced the 46 observed frequencies with an average error of 1.4%. For thiirene and isotopic derivatives, the 6-31G* IR spectra are in much better agreement with experiment than previous results with smaller bases. In particular, significantly higher frequency C–S stretches are predicted with the 6-31G* basis. Nevertheless, a few discrepancies remain between experiment and the 6-31G* SCF results. In the third study, vibrational frequencies and IR intensities of thiirene and isotopic derivatives were evaluated at the CISD level of theory using a standard DZP basis set. In the DZP-CISD thiirene spectrum, the B1 C–H out-of-plane bend and its position relative to the A1 C–S stretch differ significantly from the 6-31G* SCF results, giving confirmation of the experimental assignments. However, the same DZP-CISD force constants predict that two low-frequency bands of thiirene-d1 are assigned incorrectly. No other significant discrepancies between theory and experiment remain for the thiirene species.

Notes: The key features of the H+O3 potential energy surface have been determined using ab initio quantum mechanical methods. The electronic wave function used is a multiconfiguration Hartree–Fock wave function which provides a qualitatively correct description of various reactive channels. It is found that the H+O3→HO+O2 reaction proceeds along a nonplanar pathway in which the H atom descends vertically to the plane containing the ozone molecule to form an HO3 intermediate which then undergoes fragmentation. No planar transition state for a direct O-atom abstraction could be located. The radical–radical O+HO2 reaction was found to have no energy barrier to formation of HO3 which was determined to subsequently decompose to HO+O2. The H-atom abstraction reaction O+HO2→OH+O2 was found to have a small activation energy. The dynamical implications of these findings are discussed. The results are consistent with the observed vibrational excitation of the OH product in the H+O3 reaction. The key features of the H+O3 potential energy surface are expected to be transferable to the X+O3 systems where X=Cl, OH, NO, and NH2.

Notes: Zusammenfassung Der von Oxydkathoden ausgehende negative Ionenstrahl wurde massenspektroskopisch analysiert und ein Vergleich der Ionenkomponenten verschiedenartiger Kathoden vorgenommen. Bei der Oxydkathode treten am intensivsten die H−-, CH−-, OH−-, O 2 − - und die Cl−-Ionen auf; daneben wurden noch 11 schwächere Ionenarten beobachtet. Aus der Schärfe der mit den negativen Ionen erzeugbaren Abbildungen wurde gefolgert, daß die Ionen einen einheitlichen Entstehungsort haben. Als solcher wurde für die meisten Ionen die Kathodensubstanz ermittelt, einzig für die OH−-Ionen kommt als Herkunftsort nicht nur die Kathodensubstanz, sondern auch der Gasraum in Frage, indem OH2-Moleküle aus dem Gasraum auf die Kathodenoberfläche geraten und von dort als negative OH−-Ionen wieder emittiert werden. Der Zusammenhang zwischen der O 2 − -Emission und der Elektronenemission der Kathode wurde während der Aktivierung untersucht und durch eine Vorstellung vom Formierprozeß gedeutet: Danach besteht die Aktivierung der Kathode darin, daß Ballonen auf Grund der thermischen Dissoziation im BaO ihren regulären Platz im BaO-Gitter verlassen und an bevorzugten Stellen adsorbiert werden, wodurch sie den Charakter einer elektronenliefernden „Störstelle“ annehmen. Es wurden ferner Annahmen über den Transport der negativen Ionen vom Herkunftsort in der Kathodensubstanz bis zur Kathodenoberfläche gemacht: Während die O−-, OH−-, Cl−-Ionen durch die Ba O-Kristallite hindurch zur Kathodenoberfläche wandern, muß für die CH−- und die C 2 − -Ionen auf Grund ihres Verhaltens eine Oberflächenwanderung längs der Kristallit-Grenzflächen zur Kathodenoberfläche angenommen werden.

Notes: Summary In rats, shivering was induced by cooling. Shivering started at 36.6°C in unanaesthetized rats and at 36.0°C in animals with light pentobarbital anaesthesia (5 mg/kg i.V.). Pethidine (2 mg/kg) lowered the onset of shivering in unanaesthetized rats to 35.3 °C and in anaesthetized animals to 33.0°C. The results suggest that the effect of pethidine upon shivering is potentiated by pentobarbital.