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Complex formation, rearrangement, and reaction in PhOH Vibrational mode effects, recoil velocities, and ab initio studies
 

Summary: Complex formation, rearrangement, and reaction in PhOH¿
¿ND3:
Vibrational mode effects, recoil velocities, and ab initio studies
Richard J. Green, Ho-Tae Kim, Jun Qian, and Scott L. Anderson
Department of Chemistry, University of Utah, Salt Lake City, Utah 84112-0850
Received 22 May 2000; accepted 16 June 2000
Vibrationally mode-selected phenol cations C6H5OH and C6D5OH were reacted with ND3 in a
guided-ion-beam instrument. Integral cross sections and recoil velocity distributions are reported as
a function of collision energy and vibrational state. Three reactions are observed. A small signal is
found for the PhOH:ND3 adduct at low total energies, indicating the formation of a very
long-lived complex. The major reaction is H/D exchange, generating PhOD ND2H. Exchange is
40% efficient at low energies, strongly inhibited by collision energy, and strongly enhanced by
excitation of PhOH vibrations. Recoil velocity distributions suggest that H/D exchange proceeds
through a statistical complex at all energies. A precursor complex is invoked to explain the energy
and vibrational state dependence. The endoergic proton transfer reaction is a minor channel at all
energies, with dynamics intermediate between the direct and complex limits. Quantum chemistry
and RRKM calculations are reported, providing an additional mechanistic insight. © 2000
American Institute of Physics. S0021-9606 00 01634-2
I. INTRODUCTION
Reactions of even small polyatomic ions with small mol-

  

Source: Anderson, Scott L. - Department of Chemistry, University of Utah

 

Collections: Energy Storage, Conversion and Utilization; Materials Science; Chemistry