A photoelectron-photoion coincidence study in the ICH{sub 2}CN ion dissociation: Thermochemistry of {sup {sm{underscore}bullet}}CH{sub 2}CN, {sup +}CH{sub 2}CN, and ICH{sub 2}CN
Journal Article
·
· Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
The dissociation energies and dissociation dynamics of iodoacetonitrile (ICH{sub 2}CN) have been investigated by the photoelectron photoion coincidence (PEPICO) spectroscopy technique. The 0 K onsets for the following products were determined: {sup +}CH{sub 2}CN + I{sm{underscore}bullet}(12.188 {+-} 0.005 eV) and {sup {sm{underscore}bullet}}CH{sub 2}CN + I{sup +}(12.345 {+-} 09.010 eV). From the difference between these two values the ionization energy of the {sup {sm{underscore}bullet}}CH{sub 2}CN was found to be 10.294 {+-} 0.010 eV. By using a thermodynamic cycle that involves the gas phase acidity of CH{sub 3}CN, the electron affinity of the {sup {sm{underscore}bullet}}CH{sub 2}CN radical, and an accurate heat of formation of acetonitrile, a {Delta}{sub f}H{sup {degree}}{sub 298}(ICH{sub 2}CN) of 172.5 {+-} 4.0 kJ mol{sup {minus}1} is derived. This latter value is considerably higher than the best theoretical value of 153 kJ mol{sup {minus}1}.
- Research Organization:
- Univ. of North Carolina, Chapel Hill, NC (US)
- Sponsoring Organization:
- US Department of Energy; Natural Sciences and Engineering Research Council of Canada
- OSTI ID:
- 20017292
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 7 Vol. 104; ISSN 1089-5639; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- English
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