Avoided curve crossing between the A1 and B1 states in CF2Br2 photolysis at 234 and 265 nm

Moon Soo Park, Tae Kyu Kim, Sung Hae Lee, Kyung Hoon Jung, Hans Robert Volpp, Jürgen Wolfrum

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Abstract

The photodissociation dynamics of CF2Br2 has been studied using a two-dimensional photofragment ion image technique for the two excitation wavelengths 234 and 265 nm. At 234 nm, three dissociation channels, i.e., the radical CF2Br + Br (2PJ) (J = 1/2, 3/2), the three-body CF2 + 2Br (2PJ) (J = 1/2 3/2), and the molecular elimination channel CF2 + Br2, were observed with quantum yields of 0.84, 0.15, and trace, respectively. The difference between β (CF2Br + Br (2P3/2)) = 0.65 and β (CF2Br + Br (2P1/2)) = 0.80 suggests that the excited A1 and B1 states are strongly correlated by avoided curve crossing with a probability of 0.78. At 265 nm, the radical channel, the observed major primary dissociation channel, shows several components due to the transition close to the curve crossing point. On the basis of observations at both wavelengths, we have proposed a photodissociation dynamics model of CF2Br2 after A-band excitation.

Original languageEnglish
Pages (from-to)5606-5612
Number of pages7
JournalJournal of Physical Chemistry A
Volume105
Issue number23
DOIs
Publication statusPublished - 2001 Jun 14

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All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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