Threshold photoelectron spectroscopy of ozone

Threshold photoelectron spectrum of ozone is presented for the first time at a resolution of 21-38 meV using synchrotron radiation in the energy region of 12-21 eV. The ionization energies of the first ionized states were determined and an interpretation of the O3 spectrum with respect to its first three ionic states, 1 2A1, 1 2B2, and 1 2A2, is presented. Above 16 eV the enhancement of the intensities of the 2 2B1, 3 2A1, and 4 2B2 band systems due to the contribution of indirect processes was observed, not accessible by conventional photoelectron spectroscopy. It was also resolved and assigned the extensive vibrational structures of ozone. Between 15.5 and 18.5 eV the main band contours are similar to those found in conventional photoelectron spectroscopy, except that our threshold photoelectron spectrum reveals extensive additional vibrational structures. The band 2 2B1 was found to present an irregular vibrational spacing DeltaE, with a minimum value of 80 meV at approximately 16.47 eV.     

Etudes sur les matières végétales volatiles. CIC. Sur la structure du «diépoxyde d'allo-ocimène»

The allo-ocimene diepoxides described in our recent communication are trans (? CH?CH? ) as announced, and not cis/trans stereoisomers.     

Core excitation in O3 localized to one of two symmetry-equivalent chemical bonds: molecular alignment through vibronic coupling

Core excitation from terminal oxygen OT in O3 is shown to be an excitation from a localized core orbital to a localized valence orbital. The valence orbital is localized to one of the two equivalent chemical bonds. We experimentally demonstrate this with the Auger-Doppler effect which is observable when O3 is core excited to the highly dissociative OT1s(-1)7a1 1 state. Auger electrons emitted from the atomic oxygen fragment carry information about the molecular orientation relative to the electromagnetic-field vector at the moment of excitation. The data together with analytical functions for the electron-peak profiles give clear evidence that the preferred molecular orientation for excitation only depends on the orientation of one bond, not on the total molecular orientation. The localization of the valence orbital "7a1" is caused by mixing of the valence orbital "5b2" through vibronic coupling of antisymmetric stretching mode with b2 symmetry. To the best of our knowledge, it is the first discussion of the localization of a core excitation of O3. This result explains the success of the widely used assumption of localized core excitation in adsorbates and large molecules.     

The electronic structure of free water clusters probed by Auger electron spectroscopy

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.     

Rhodium(II)-Catalyzed Selective C(sp3)−H Amination of Alkanes

The development of an efficient catalytic system enabling the conversion of alkanes to valuable nitrogen-containing building blocks is reported. Light alkanes can be selectively functionalized by an intermolecular C(sp³)−H amination reaction that proceeds at room temperature in the presence of only 1 mol % of a dirhodium(II) complex. Selective amination of tertiary C(sp³)−H within acyclic or cyclic alkanes used as limiting components leads to the corresponding amides isolated with yields in the 51–96 % range. The reaction, that can be performed on a gram-scale, applies with equal levels of efficiency and selectivity to more complex hydrocarbons.