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Atmospheric nucleation precursors catalyzed isomerization of CH2SH to CH3S: mechanisms and topological analysis

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Abstract

The isomerization of CH2SH to CH3S in the absence and presence of atmospheric nucleation precursors (H2O, HCOOH, and H2SO4) has been investigated at the G3XMP2//B3LYP/6–311+G(3df,2p) level. It is shown that the barrier heights for the isomerization are 28.74, 6.45, 12.96, and 19.23 kcal mol−1, when the isomerization is performed in gas phase and with sulfuric acid, water, and formic acid as a precursor, respectively. The rate constants of the isomerization are calculated using the transition state theory with the Wigner tunneling correction over the temperature range of 298–800 K. The rate constant of sulfuric acid-catalyzed isomerization is 1.46 × 103 times at 298 K larger than that in gas phase. Sulfuric acid-catalyzed isomerization is expected to be favorable under atmospheric condition. Moreover, topology analysis has been carried out to characterize the nature of interactions in the isomerization. Enthalpies of formation (∆f H °298K ), entropies (S °298K ), and heat capacities (C p) of all the stabilized species have been calculated using CBS-QB3 method. These results can be used for atmosphere sulfur cycle modeling application.

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Acknowledgments

We thank the School of Chemistry & Chemical engineering of Shaanxi Normal University for access to the high performance computing service. This work is supported by the foundation of Shaanxi Education Department (2013JK0667), the foundation of Yan’an University (YDQ2013-16), and the foundation of College of Chemistry & Chemical engineering of Yan’an university (YDHG2014-Z04).

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Authors and Affiliations

  1. College of Chemistry & Chemical engineering, Yan’an University, Yan’an, 716000, Shaanxi, China

    Jia Cao, Zhi Xiang Wang, Lou Jun Gao & Feng Fu

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  1. Jia Cao
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  2. Zhi Xiang Wang
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  3. Lou Jun Gao
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  4. Feng Fu
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Correspondence to Jia Cao.

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11224_2014_489_MOESM1_ESM.doc

Supplementary material 1 (DOC 672 kb) Appendix A. Supplementary data Optimized geometries of all the species at the B3LYP/6-311+G(3df,2p) level are given in Fig. S1. The molecular graphs of the transition states and intermediates calculated using B3LYP/6-311+G(3df,2p) method are shown in Fig. S2. The zero point energies (ZPE) and electronic energies (E) of all the species are listed in Table S1. The predicted ratios of rate over the temperature range of 298~800 K are listed in Table S2.

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Cao, J., Wang, Z.X., Gao, L.J. et al. Atmospheric nucleation precursors catalyzed isomerization of CH2SH to CH3S: mechanisms and topological analysis. Struct Chem 26, 261–268 (2015). https://doi.org/10.1007/s11224-014-0489-0

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  • DOI: https://doi.org/10.1007/s11224-014-0489-0

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