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UV-spectroscopy, electronic structure and ozonolytic reactivity of sesquiterpenes: a theoretical study

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Abstract

Sesquiterpenes, one of the most important classes of biogenic volatile organic compounds, are potentially significant precursors to secondary organic aerosols (SOAs) in nature. The electronic structure of sesquiterpenes and their reactivity in the ozonolysis reaction were investigated by density functional theory. Results from the CIS calculations combined with an analysis of transition intensities show that the first peaks in the ultraviolet (UV) spectra for saturated and unsaturated isomers are σ–σ* and π–π* transitions, respectively. The UV absorption wavelength and absorbency are dictated by the electronic structures of these compounds. An increase in the number of double bonds and formation of a conjugated system expand the range of absorption in the UV region. An isomer with an endocyclic C = C bond presents weaker UV transition intensity than its corresponding exocyclic isomer. Results from conceptual DFT chemical reactivity indices of isomers suggest that no quantitative linear relationships between the structural changes and their reactivity, such as different degrees of unsaturated C = C double bonds, or the number of substituents attached to the C = C bond were discovered. In the ozonolysis reaction of sesquiterpenes, isomers with larger steric hindrance of substituents or endocyclic C = C bond possess higher chemical reactivity compared to isomers with smaller steric hindrandce or with an exocyclic C = C bond. These results are imperative to a better understanding of SOAs production mechanisms in the troposphere.

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Acknowledgments

Financial support from the Earmarked Fund of the State Key Laboratory of Organic Geochemistry (No. SKLOG2009A04) and the National Natural Science Foundation of China (Nos. 40821003, 20733002 and 20873008) is greatly appreciated. The authors gratefully thank Dr. Liang Peng of the Department of Chemistry and Environment, South China Normal University for useful suggestions and stimulated discussions. This is contribution No. IS-1357 from GIGCAS.

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Authors and Affiliations

  1. State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, 510640, China

    Shu-Xian Hu & Eddy Yongping Zeng

  2. College of Chemistry, Beijing Normal University, Beijing, 100875, China

    Jian-Guo Yu

  3. Graduate School of the Chinese Academy of Sciences, Beijing, 100049, China

    Shu-Xian Hu

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  1. Shu-Xian Hu
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  2. Jian-Guo Yu
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  3. Eddy Yongping Zeng
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Correspondence to Eddy Yongping Zeng.

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Hu, SX., Yu, JG. & Zeng, E.Y. UV-spectroscopy, electronic structure and ozonolytic reactivity of sesquiterpenes: a theoretical study. J Mol Model 18, 1455–1462 (2012). https://doi.org/10.1007/s00894-011-1160-y

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