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Title: Formation of HONO from the NH3-promoted hydrolysis of NO2 dimers in the atmosphere

Abstract

One challenging issue in atmospheric chemistry is identifying the source of nitrous acid (HONO), which is believed to be a primary source of atmospheric “detergent” OH radicals. Herein, we show a reaction route for the formation of HONO species from the NH3-promoted hydrolysis of a NO2 dimer (ONONO2), which entails a low free-energy barrier of 0.5 kcal/mol at room temperature. Our systematic study of HONO formation based on NH3 + ONONO2 + nH2O and water droplet systems with the metadynamics simulation method and a reaction pathway searching method reveals two distinct mechanisms: (i) In monohydrates (n = 1), tetrahydrates (n = 4), and water droplets, only one water molecule is directly involved in the reaction (denoted the single-water mechanism); and (ii) the splitting of two neighboring water molecules is seen in the dihydrates (n = 2) and trihydrates (n = 3) (denoted the dual-water mechanism). A comparison of the computed free-energy surface for NH3-free and NH3-containing systems indicates that gaseous NH3can markedly lower the free-energy barrier to HONO formation while stabilizing the product state, producing a more exergonic reaction, in contrast to the endergonic reaction for the NH3-free system. More importantly, the water droplet reduces the free-energy barrier for HONOmore » formation to 0.5 kcal/mol, which is negligible at room temperature. We show that the entropic contribution is important in the mechanism by which NH3 promotes HONO formation. Furthermore, this study provides insight into the importance of fundamental HONO chemistry and its broader implication to aerosol and cloud processing chemistry at the air–water interface.« less

Authors:
 [1];  [2];  [3];  [4];  [2];  [4];  [5]
+ Show Author Affiliations
  1. Univ. of Nebraska-Lincoln, Lincoln, NE (United States); The Univ. of Texas at Austin, Austin, TX (United States)
  2. The Univ. of Texas at Austin, Austin, TX (United States)
  3. Beijing Univ. of Chemical Technology, Beijing (China)
  4. Univ. of Nebraska-Lincoln, Lincoln, NE (United States)
  5. Univ. of Nebraska-Lincoln, Lincoln, NE (United States); Beijing Univ. of Chemical Technology, Beijing (China)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE
OSTI Identifier:
1543913
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 28; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology; Other Topics; air–water interface; HONO; NO2 dimer

Citation Formats

Li, Lei, Duan, Zhiyao, Li, Hui, Zhu, Chongqin, Henkelman, Graeme, Francisco, Joseph S., and Zeng, Xiao Cheng. Formation of HONO from the NH3-promoted hydrolysis of NO2 dimers in the atmosphere. United States: N. p., 2018. Web. doi:10.1073/pnas.1807719115.
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Li, Lei, Duan, Zhiyao, Li, Hui, Zhu, Chongqin, Henkelman, Graeme, Francisco, Joseph S., & Zeng, Xiao Cheng. Formation of HONO from the NH3-promoted hydrolysis of NO2 dimers in the atmosphere. United States. https://doi.org/10.1073/pnas.1807719115
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Li, Lei, Duan, Zhiyao, Li, Hui, Zhu, Chongqin, Henkelman, Graeme, Francisco, Joseph S., and Zeng, Xiao Cheng. Mon . "Formation of HONO from the NH3-promoted hydrolysis of NO2 dimers in the atmosphere". United States. https://doi.org/10.1073/pnas.1807719115. https://www.osti.gov/servlets/purl/1543913.
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@article{osti_1543913,
title = {Formation of HONO from the NH3-promoted hydrolysis of NO2 dimers in the atmosphere},
author = {Li, Lei and Duan, Zhiyao and Li, Hui and Zhu, Chongqin and Henkelman, Graeme and Francisco, Joseph S. and Zeng, Xiao Cheng},
abstractNote = {One challenging issue in atmospheric chemistry is identifying the source of nitrous acid (HONO), which is believed to be a primary source of atmospheric “detergent” OH radicals. Herein, we show a reaction route for the formation of HONO species from the NH3-promoted hydrolysis of a NO2 dimer (ONONO2), which entails a low free-energy barrier of 0.5 kcal/mol at room temperature. Our systematic study of HONO formation based on NH3 + ONONO2 + nH2O and water droplet systems with the metadynamics simulation method and a reaction pathway searching method reveals two distinct mechanisms: (i) In monohydrates (n = 1), tetrahydrates (n = 4), and water droplets, only one water molecule is directly involved in the reaction (denoted the single-water mechanism); and (ii) the splitting of two neighboring water molecules is seen in the dihydrates (n = 2) and trihydrates (n = 3) (denoted the dual-water mechanism). A comparison of the computed free-energy surface for NH3-free and NH3-containing systems indicates that gaseous NH3can markedly lower the free-energy barrier to HONO formation while stabilizing the product state, producing a more exergonic reaction, in contrast to the endergonic reaction for the NH3-free system. More importantly, the water droplet reduces the free-energy barrier for HONO formation to 0.5 kcal/mol, which is negligible at room temperature. We show that the entropic contribution is important in the mechanism by which NH3 promotes HONO formation. Furthermore, this study provides insight into the importance of fundamental HONO chemistry and its broader implication to aerosol and cloud processing chemistry at the air–water interface.},
doi = {10.1073/pnas.1807719115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 28,
volume = 115,
place = {United States},
year = {Mon Jun 25 00:00:00 EDT 2018},
month = {Mon Jun 25 00:00:00 EDT 2018}
}
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https://doi.org/10.1073/pnas.1807719115
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    Theoretical Investigation of the Photoexcited NO 2 +H 2 O reaction at the Air–Water Interface and Its Atmospheric Implications
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    • Martins‐Costa, Marilia T. C.; Anglada, Josep M.; Francisco, Joseph S.
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    The effect of water on the heterogeneous reactions of SO 2 and NH 3 on the surfaces of α-Fe 2 O 3 and γ-Al 2 O 3
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