The multiplexed chemical kinetic photoionization mass spectrometer: A new approach to isomer-resolved chemical kinetics (original) (raw)
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Research Article| October 31 2008
1Combustion Research Facility, Mail Stop 9055,
Sandia National Laboratories
, Livermore, California 94551-0969,
USA
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1Combustion Research Facility, Mail Stop 9055,
Sandia National Laboratories
, Livermore, California 94551-0969,
USA
Search for other works by this author on:
1Combustion Research Facility, Mail Stop 9055,
Sandia National Laboratories
, Livermore, California 94551-0969,
USA
Search for other works by this author on:
1Combustion Research Facility, Mail Stop 9055,
Sandia National Laboratories
, Livermore, California 94551-0969,
USA
Search for other works by this author on:
1Combustion Research Facility, Mail Stop 9055,
Sandia National Laboratories
, Livermore, California 94551-0969,
USA
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2Research Center for Chemical Kinetics, Department of Chemistry,
The Catholic University of America
, Washington, DC 20064,
USA
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3Department of Chemistry,
Texas A&M University
, P.O. Box 30012, College Station, Texas 77842,
USA
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4Chemical Sciences Division,
Ernest Orlando Lawrence Berkeley National Laboratory
, Berkeley, California 94720,
USA
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4Chemical Sciences Division,
Ernest Orlando Lawrence Berkeley National Laboratory
, Berkeley, California 94720,
USA
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4Chemical Sciences Division,
Ernest Orlando Lawrence Berkeley National Laboratory
, Berkeley, California 94720,
USA
5Departments of Chemistry and Physics,
University of California
, Berkeley, California 94720,
USA
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Rev. Sci. Instrum. 79, 104103 (2008)
We have developed a multiplexed time- and photon-energy–resolved photoionization mass spectrometer for the study of the kinetics and isomeric product branching of gas phase, neutral chemical reactions. The instrument utilizes a side-sampled flow tube reactor, continuously tunable synchrotron radiation for photoionization, a multimass double-focusing mass spectrometer with 100% duty cycle, and a time- and position-sensitive detector for single ion counting. This approach enables multiplexed, universal detection of molecules with high sensitivity and selectivity. In addition to measurement of rate coefficients as a function of temperature and pressure, different structural isomers can be distinguished based on their photoionization efficiency curves, providing a more detailed probe of reaction mechanisms. The multiplexed three-dimensional data structure (intensity as a function of molecular mass, reaction time, and photoionization energy) provides insights that might not be available in serial acquisition, as well as additional constraints on data interpretation.
REFERENCES
L. F.
Wilhelmy
,
Ann. Phys. Chem.
157
,
413
(
1850
).
G.
Porter
,
Proc. R. Soc. London, Ser. A
200
,
284
(
1950
).
The phenomenal success of gas chromatography/mass spectrometry instruments applied to analysis of complex chemical mixtures relies on chemical separation (by chromatography) into pure components followed by 70 eV electron-bombardment mass spectrometry. This powerful technique is nevertheless unsuitable for our purposes due to its slow time response.
G.
Capozza
,
E.
Segoloni
,
F.
Leonori
,
G. G.
Volpi
, and
P.
Casavecchia
,
J. Chem. Phys.
120
,
4557
(
2004
).
I. R.
Slagle
,
F.
Yamada
, and
D.
Gutman
,
J. Am. Chem. Soc.
103
,
149
(
1981
).
I. R.
Slagle
and
D.
Gutman
,
J. Am. Chem. Soc.
107
,
5342
(
1985
).
C.
Fockenberg
,
H. J.
Bernstein
,
G. E.
Hall
,
J. T.
Muckerman
,
J. M.
Preses
,
T. J.
Sears
, and
R. E.
Weston
, Jr.,
Rev. Sci. Instrum.
70
,
3259
(
1999
).
M. A.
Blitz
,
A.
Goddard
,
T.
Ingham
, and
M. J.
Pilling
,
Rev. Sci. Instrum.
78
,
034103
(
2007
).
M. P.
Sinha
and
M.
Wadsworth
,
Rev. Sci. Instrum.
76
,
025103
(
2005
).
J.
Mattauch
,
Phys. Rev.
50
,
617
(
1936
).
C. A.
Taatjes
,
N.
Hansen
,
D. L.
Osborn
,
K.
Kohse-Hoeinghaus
,
T. A.
Cool
, and
P. R.
Westmoreland
,
Phys. Chem. Chem. Phys.
10
,
20
(
2008
).
G.
Meloni
,
P.
Zou
,
S. J.
Klippenstein
,
M.
Ahmed
,
S. R.
Leone
,
C. A.
Taatjes
, and
D. L.
Osborn
,
J. Am. Chem. Soc.
128
,
13559
(
2006
).
F.
Goulay
,
D. L.
Osborn
,
C. A.
Taatjes
,
P.
Zou
,
G.
Meloni
, and
S. R.
Leone
,
Phys. Chem. Chem. Phys.
9
,
4291
(
2007
).
G.
Meloni
,
T. M.
Selby
,
F.
Goulay
,
S. R.
Leone
,
D. L.
Osborn
, and
C. A.
Taatjes
,
J. Am. Chem. Soc.
129
,
14019
(
2007
).
C. J.
Howard
,
J. Phys. Chem.
83
,
3
(
1979
).
J.
Brunning
and
L. J.
Stief
,
J. Chem. Phys.
84
,
4371
(
1986
).
P. A.
Heimann
,
M.
Koike
,
C. W.
Hsu
,
D.
Blank
,
X. M.
Yang
,
A. G.
Suits
,
Y. T.
Lee
,
M.
Evans
,
C. Y.
Ng
,
C.
Flaim
, and
H. A.
Padmore
,
Rev. Sci. Instrum.
68
,
1945
(
1997
).
J. V.
Vallerga
and
O. H. W.
Siegmund
,
Nucl. Instrum. Methods Phys. Res. A
442
,
159
(
2000
).
D. W.
Minsek
and
P.
Chen
,
J. Phys. Chem.
94
,
8399
(
1990
).
T.
Zhang
,
X. N.
Tang
,
K. C.
Lau
,
C. Y.
Ng
,
C.
Nicolas
,
D. S.
Peterka
,
M.
Ahmed
,
M. L.
Morton
,
B.
Ruscic
,
R.
Yang
,
L. X.
Wei
,
C. Q.
Huang
,
B.
Yang
,
J.
Wang
,
L. S.
Shen
,
Y. W.
Zhang
, and
F.
Qi
,
J. Chem. Phys.
124
,
074302
(
2006
).
D. L.
Osborn
,
P.
Zou
,
T. M.
Selby
,
F.
Goulay
,
G.
Meloni
,
A.
Fahr
, and
C. A.
Taatjes
(unpublished).
F.
Goulay
,
A. J.
Trevitt
,
G.
Meloni
,
T. M.
Selby
,
D. L.
Osborn
,
C. A.
Taatjes
,
L.
Vereecken
, and
S. R.
Leone
, “
Cyclic versus linear isomers produced by reaction of the methylidyne radical (CH) with small unsaturated hydrocarbons
,”
J. Am. Chem. Soc.
(submitted).
W. M.
Howard
,
Phys. Fluids
4
,
521
(
1961
).
W. L.
Hsu
and
D. M.
Tung
,
Rev. Sci. Instrum.
63
,
4138
(
1992
).
Units used in this equation are the same as in Fig. 6.
C. A.
Taatjes
,
Int. J. Chem. Kinet.
39
,
565
(
2007
).
S. B.
Moore
and
R. W.
Carr
,
Int. J. Mass Spectrom. Ion Phys.
24
,
161
(
1977
).
T. M.
Selby
,
G.
Meloni
,
F.
Goulay
,
S. R.
Leone
,
A.
Fahr
,
C. A.
Taatjes
, and
D. L.
Osborn
,
J. Phys. Chem. A
112
,
9366
(
2008
).
G. R.
Ho
,
M. S.
Lin
,
Y. L.
Wang
, and
T. W.
Change
,
J. Chem. Phys.
109
,
5868
(
1998
).
D. M. P.
Holland
and
D. A.
Shaw
,
Chem. Phys.
243
,
333
(
1999
).
© 2008 American Institute of Physics.
2008
American Institute of Physics
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