Theoretical and infrared spectroscopic investigation of the O(2) (-).benzene and O(4) (-).benzene complexes

J Chem Phys. 2007 Aug 28;127(8):084319. doi: 10.1063/1.2759929.

Abstract

The infrared spectra of the O(2) (-).benzene and O(4) (-).benzene complexes are determined by means of Ar predissociation spectroscopy. Several transitions due to CH stretch fundamentals and various combination bands are observed in the 2700-3100 cm(-1) region. The experimental results are interpreted with the aid of electronic structure calculations. A comparison of the calculated and experimental spectra reveals that the spectrum of O(2) (-).benzene most likely arises from an isomer where the superoxide molecule binds preferentially to one CH group of benzene. In contrast, the spectrum of O(4) (-).benzene yields a CH pattern remarkably similar to that displayed by the C(2nu) X(-).benzene (X=halogen) complexes, consistent with a structure with two CH groups equally involved in the bonding. The lower energy vibrational fundamental transitions of the O(4) (-) anion are recovered with a slight redshift in the O(4) (-).benzene spectrum, establishing that this charge-delocalized dimer ion retains its identity upon complexation.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.