Reversible reactions of cycloalkane solvent holes. 2. Scavenging of cis- and trans-decalin{sup {sm_bullet}+} by benzene
Solvent holes in liquid cis- and trans-decalin form metastable complexes with benzene, which are probably solvation complexes of monomer radical cations of benzene. At 25 C, the rate constants of formation of the complexes are, for trans- and cis-decalin respectively 1.1 x 10{sup 11} and 3.6 x 10{sup 10} M{sup {minus}1} s{sup {minus}1}, and the natural lifetime of the complex is 7 ns for trans- and 50 ns for cis-decalin. Thermodynamic potentials for the complexation are determined. The heat of the complex formation is {approx}{minus}26 kJ/mol for trans- and {approx}{minus}18 kJ/mol for cis-decalin. In cis-decalin, the complexes are more stable because of near-zero entropy of the complex formation. The complex decays by proton or H atom transfer with activation energy {approx}10 kJ/mol (which yields a benzonium cation) or in a reactive encounter with a second benzene molecule (which yields a benzene dimer cation). Laser excitation of the dimer cation with a 1.165- or 2.33 eV photon causes valence band electron transfer and injection of a free solvent hole.
- Research Organization:
- Argonne National Lab., IL (US)
- Sponsoring Organization:
- US Department of Energy
- DOE Contract Number:
- W-31109-ENG-38
- OSTI ID:
- 20030686
- Journal Information:
- Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 15 Vol. 104; ISSN 1089-5647; ISSN JPCBFK
- Country of Publication:
- United States
- Language:
- English
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