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The Power of Accurate Energetics (or Thermochemistry: What is it Good for?)

  • Critical Insight
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Journal of The American Society for Mass Spectrometry

Abstract

The utility of measuring the energetics of ion-molecule reactions is discussed. After distinguishing between the terms of thermodynamics (macroscopic, equilibrium quantities) and energetics (microscopic and kinetically relevant quantities), the potential energy surfaces for ion-molecule reactions are reviewed and their implications discussed. Equations describing the kinetic energy dependence of ion-molecule reactions are introduced and the effects of entropy on reaction rates and branching ratios are discussed. Several case histories allow an exploration of the utility of accurate thermochemical information and probe how accurate such energetic information must be to be predictive. These case studies include decomposition of hydrated metal dications, the reaction of FeO+ with H2, and fragmentation of a small protonated peptide (GG). These illustrate a range of interesting systems for which accurate energetic information has been influential in understanding the observed reactivity. Comparisons with theory demonstrate that experimental information is still required for truly predictive capability.

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Acknowledgment

While ion chemistry may occur in a vacuum, research does not. I thank my students for their many contributions to the work here and for teaching me many new things over the years. Students contributing to the examples illustrated here include T. E. Hofstetter (ne Cooper), D. E. Clemmer, Y.-M. Chen, F. A. Khan, and A. L. Heaton. The National Science Foundation (CHE-1049580) and Department of Energy, Office of Basic Energy Sciences have provided financial support for our work. I thank Carol Robinson for the opportunity to pontificate here.

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  1. Department of Chemistry, University of Utah, Salt Lake City, UT, USA

    P. B. Armentrout

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Armentrout, P.B. The Power of Accurate Energetics (or Thermochemistry: What is it Good for?). J. Am. Soc. Mass Spectrom. 24, 173–185 (2013). https://doi.org/10.1007/s13361-012-0515-7

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  • DOI: https://doi.org/10.1007/s13361-012-0515-7

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