The Cr(+)-D(2) cation complex: Accurate experimental dissociation energy, intermolecular bond length, and vibrational parameters

J Chem Phys. 2009 Oct 28;131(16):164303. doi: 10.1063/1.3250985.

Abstract

The infrared spectrum of the T-shaped (52)Cr(+)-D(2) complex is measured over the 2742-2820 cm(-1) range by detecting Cr(+) photofragments. The main band, due to the D-D stretch excitation, is shifted at 215 cm(-1) to lower energy from the Q(0) (1) transition of the free D(2) molecule and displays clearly resolved rovibrational transitions. Observation of a photodissociation onset for the N(')=8 rotational level is used to infer that the dissociation energy of Cr(+)-D(2), with respect to ground-state Cr(+) and D(2) fragments, lies between 2839.7 and 2856.9 cm(-1). Perturbations to the upper state levels are presumed to arise from interactions with quasibound combination levels involving the intermolecular stretch and bend vibrational modes. A vibrationally averaged Cr(+)...D(2) separation of 2.023 A and an estimate of 394 cm(-1) for the intermolecular harmonic stretching frequency are derived from the measured rotational constants.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Chromium / chemistry*
  • Deuterium / chemistry*
  • Spectrophotometry, Infrared
  • Thermodynamics
  • Vibration*

Substances

  • Chromium
  • Deuterium