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

David L. Osborn;

1Combustion Research Facility, Mail Stop 9055,

Sandia National Laboratories

, Livermore, California 94551-0969,

USA

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Peng Zou;

1Combustion Research Facility, Mail Stop 9055,

Sandia National Laboratories

, Livermore, California 94551-0969,

USA

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Howard Johnsen;

1Combustion Research Facility, Mail Stop 9055,

Sandia National Laboratories

, Livermore, California 94551-0969,

USA

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Carl C. Hayden;

1Combustion Research Facility, Mail Stop 9055,

Sandia National Laboratories

, Livermore, California 94551-0969,

USA

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Craig A. Taatjes;

1Combustion Research Facility, Mail Stop 9055,

Sandia National Laboratories

, Livermore, California 94551-0969,

USA

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Vadim D. Knyazev;

2Research Center for Chemical Kinetics, Department of Chemistry,

The Catholic University of America

, Washington, DC 20064,

USA

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Simon W. North;

3Department of Chemistry,

Texas A&M University

, P.O. Box 30012, College Station, Texas 77842,

USA

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Darcy S. Peterka;

4Chemical Sciences Division,

Ernest Orlando Lawrence Berkeley National Laboratory

, Berkeley, California 94720,

USA

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Musahid Ahmed;

4Chemical Sciences Division,

Ernest Orlando Lawrence Berkeley National Laboratory

, Berkeley, California 94720,

USA

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Stephen R. Leone

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.

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© 2008 American Institute of Physics.

2008

American Institute of Physics

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