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, 79 (10), 104103

The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach to Isomer-Resolved Chemical Kinetics

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The Multiplexed Chemical Kinetic Photoionization Mass Spectrometer: A New Approach to Isomer-Resolved Chemical Kinetics

David L Osborn et al. Rev Sci Instrum.

Abstract

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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