Vibrationally induced electron detachment. A rate for electron loss from vibrationally excited acetone enolate anion

Robert F. Foster, William Tumas, John I. Brauman

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Abstract

A rate for electron autodetachment from vibrationally excited acetone enolate anion in the gas phase has been deduced experimentally from the observation of photochemical branching between an adiabatic fragmentation channel and a nonadiabatic vibrationally induced electron detachment channel under collisionless conditions using ion cyclotron resonance spectrometry. Infrared multiple-photon activation of acetone enolate anion with a pulsed CO2 laser results in both methane elimination to produce deprotonated ketene anion and electron detachment. These results coupled with thermochemical and mechanistic considerations as well as statistical reaction rate theory calculations lead to an estimated rate for electron autodetachment from the vibrationally excited anion of 107 s-1 at an energy ca. 1 eV above threshold. The experimental details as well as the calculations and modeling involved in this determination are presented along with an evaluation of proposed models for vibrational-to-electronic coupling.

Original languageEnglish
Pages (from-to)61-68
Number of pages8
JournalJournal of Physical Chemistry
Volume93
Issue number1
Publication statusPublished - 1989

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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