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Photodissociation of CH2ICH2I, CF2ICF2I, and CF2BrCF2I in solution

Rasmusson, M; Tarnovsky, Alexander LU ; Pascher, Torbjörn LU ; Sundström, Villy LU and Åkesson, Eva LU (2002) In The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory 106(31). p.7090-7098
Abstract
The photodissociation dynamics of CH2ICH2I, CF2ICF2I, and CF2BrCF2I have been studied in solution after excitation at 266 nm. Formation of I-2 is apparent within tens of picoseconds in solutions of CH2ICH2I and CF2ICF2I in acetonitrile. but not from CF2BrCF2I, More I-2 is formed from CH2ICH2I rather than from CF2-ICF2I, as expected if the 12 formation is a result of secondary dissociation of the haloethyl radicals followed by geminate combination. For CH2ICH2I, the 12 formation is ultrafast (<2 ps) in several different solvents. The quantum yields Of 12 formation (after a few microseconds) were found to be 1.0+/-0.1 for CH2ICH2I and 0.75-0.95 for CF2ICF2I in hexane, dichloromethane, and tetrachloromethane. The data on a nanosecond to... (More)
The photodissociation dynamics of CH2ICH2I, CF2ICF2I, and CF2BrCF2I have been studied in solution after excitation at 266 nm. Formation of I-2 is apparent within tens of picoseconds in solutions of CH2ICH2I and CF2ICF2I in acetonitrile. but not from CF2BrCF2I, More I-2 is formed from CH2ICH2I rather than from CF2-ICF2I, as expected if the 12 formation is a result of secondary dissociation of the haloethyl radicals followed by geminate combination. For CH2ICH2I, the 12 formation is ultrafast (<2 ps) in several different solvents. The quantum yields Of 12 formation (after a few microseconds) were found to be 1.0+/-0.1 for CH2ICH2I and 0.75-0.95 for CF2ICF2I in hexane, dichloromethane, and tetrachloromethane. The data on a nanosecond to microsecond time scale indicate that all haloethyl radicals decay within tens of nanoseconds. We suggest that the decay of haloethyl radicals can occur partially via abstraction. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
volume
106
issue
31
pages
7090 - 7098
publisher
The American Chemical Society
external identifiers
  • wos:000177314300003
  • scopus:0037044072
ISSN
1520-5215
DOI
10.1021/jp020720n
language
English
LU publication?
yes
id
bf578356-7a7f-4716-899d-64c14933f6d0 (old id 331966)
date added to LUP
2007-11-09 14:15:46
date last changed
2017-07-02 04:15:35
@article{bf578356-7a7f-4716-899d-64c14933f6d0,
  abstract     = {The photodissociation dynamics of CH2ICH2I, CF2ICF2I, and CF2BrCF2I have been studied in solution after excitation at 266 nm. Formation of I-2 is apparent within tens of picoseconds in solutions of CH2ICH2I and CF2ICF2I in acetonitrile. but not from CF2BrCF2I, More I-2 is formed from CH2ICH2I rather than from CF2-ICF2I, as expected if the 12 formation is a result of secondary dissociation of the haloethyl radicals followed by geminate combination. For CH2ICH2I, the 12 formation is ultrafast (&lt;2 ps) in several different solvents. The quantum yields Of 12 formation (after a few microseconds) were found to be 1.0+/-0.1 for CH2ICH2I and 0.75-0.95 for CF2ICF2I in hexane, dichloromethane, and tetrachloromethane. The data on a nanosecond to microsecond time scale indicate that all haloethyl radicals decay within tens of nanoseconds. We suggest that the decay of haloethyl radicals can occur partially via abstraction.},
  author       = {Rasmusson, M and Tarnovsky, Alexander and Pascher, Torbjörn and Sundström, Villy and Åkesson, Eva},
  issn         = {1520-5215},
  language     = {eng},
  number       = {31},
  pages        = {7090--7098},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory},
  title        = {Photodissociation of CH2ICH2I, CF2ICF2I, and CF2BrCF2I in solution},
  url          = {http://dx.doi.org/10.1021/jp020720n},
  volume       = {106},
  year         = {2002},
}