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Calculated ionization energies for a series of sesquiterpenes: comparisons with experimental vertical ionization energies and comments on related structure–activity relationships (SARs)

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Abstract

The energies of the highest-occupied molecular orbitals (HOMOs) are known to be excellent predictors of the reactivities of biogenic hydrocarbons, such as terpenes, with reactive atmospheric oxidants including O3, OH, and NO3. Structure–Activity Relationships (SARs) have also been effectively employed in such studies and related to HOMO energies and lowest ionization energies (ionization potentials). This study employs density function theory (DFT), at the B3LYP/6-31G** level, to predict vertical ionization energies (IPv) for a structurally diverse group of sesquiterpenes, each of which has been reported in air samples collected in the lower troposphere. The availability of published UV photoelectron spectra for nine sesquiterpenes permits comparison of experimental and theoretical vertical ionization energy data. The experimental and theoretical data show a good correlation (average discrepancy ± 0.07 eV). This enables predictions of reactivities for sesquiterpenes whose tropospheric lifetimes may last only a few hours before their transformations into secondary organic aerosols (SOA) close to their emission sources.

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Acknowledgment

Arthur Greenberg wishes to acknowledge the helpful discussions with Professors Barkley C. Sive (University of New Hampshire), and Robert J. Griffin (Rice University), which stimulated this research.

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Authors and Affiliations

  1. Department of Pathology, Analytical Chemistry Core (ACC), University of Texas Medical Branch at Galveston, Galveston, TX, 77555-0438, USA

    Dhananjaya Nauduri

  2. Department of Chemistry, University of New Hampshire, Durham, NH, 03824, USA

    Arthur Greenberg

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  1. Dhananjaya Nauduri
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  2. Arthur Greenberg
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Correspondence to Arthur Greenberg.

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Nauduri, D., Greenberg, A. Calculated ionization energies for a series of sesquiterpenes: comparisons with experimental vertical ionization energies and comments on related structure–activity relationships (SARs). Struct Chem 20, 417–421 (2009). https://doi.org/10.1007/s11224-009-9431-2

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  • DOI: https://doi.org/10.1007/s11224-009-9431-2

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