Threshold Photoelectron Spectroscopy of Cyclopropenylidene, Chlorocyclopropenylidene, and Their Deuterated Isotopomeres - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2010

Threshold Photoelectron Spectroscopy of Cyclopropenylidene, Chlorocyclopropenylidene, and Their Deuterated Isotopomeres

Patrick Hemberger
  • Fonction : Auteur
Bastian Noller
  • Fonction : Auteur
Michael Steinbauer
  • Fonction : Auteur
Ingo Fischer
  • Fonction : Auteur
Bárbara Cunha de Miranda
  • Fonction : Auteur
Gustavo Garcia
  • Fonction : Auteur

Résumé

Cyclopropenylidene (c-C3H2), chlorocyclopropenylidene (c-C3HCl), and their deuterated isotopomers were studied by the threshold photoelectron-photoion coincidence (TPEPICO) technique using VUV synchrotron radiation. The carbenes were generated via flash pyrolysis. In all species a change in geometry is visible upon ionization, with significant activity in the C═C, C—C-stretching mode and, in the case of c-C3H2/D2, the C—H-bending mode. The electron is removed from an sp2 like hybrid orbital centered on the carbene C atom. The mass selected threshold photoelectron (TPE) spectra were fitted by a Franck−Condon simulation, yielding the equilibrium geometry of the cation ground state (1A1). The adiabatic ionization energy IEad of c-C3H2 was determined to be 9.17 eV, in good agreement with calculations and literature values. Two vibrational wavenumbers of the cation were determined experimentally (ν3+ = 1150 cm−1 and ν2+ = 1530 cm−1). Chlorocyclopropenylidene was also studied by TPE spectroscopy and has a similar IEad of 9.17 eV. The spectrum also shows a vibrational progression that corresponds to the C═C- and C—C-stretching modes of the cation. The equilibrium geometry was also determined by a Franck−Condon fit. The IEad of the deuterated isotopomers, c-C3D2 and c-C3DCl, were also determined to be 9.17 eV. The spectra confirm the assignments for the nondeuterated species.
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hal-04155816 , version 1 (07-07-2023)

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Patrick Hemberger, Bastian Noller, Michael Steinbauer, Ingo Fischer, Christian Alcaraz, et al.. Threshold Photoelectron Spectroscopy of Cyclopropenylidene, Chlorocyclopropenylidene, and Their Deuterated Isotopomeres. Journal of Physical Chemistry A, 2010, 114 (42), pp.11269-11276. ⟨10.1021/jp104019d⟩. ⟨hal-04155816⟩
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