Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

Yu Xia; Bo Long; Ai Liu; Donald G. Truhlar

doi:10.1016/j.fmre.2023.02.012

Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

Yu Xia, Bo Long, Ai Liu, Donald G. Truhlar

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4 Scopus citations

Abstract

Atmospheric oxidation processes are of central importance in atmospheric climate models. It is often considered that volatile organic molecules are mainly removed by hydroxyl radical; however, the kinetics of some reactions of hydroxyl radical with volatile organic molecules are slow. Here we report rate constants for rapid reactions of formyl fluoride with Criegee intermediates. These rate constants are calculated by dual-level multistructural canonical variational transition state theory with small-curvature tunneling (DL-MS-CVT/SCT). The treatment contains beyond-CCSD(T) electronic structure calculations for transition state theory, and it employs validated density functional input for multistructural canonical variational transition state theory with small-curvature tunneling and for variable-reaction-coordinate variational transition state theory. We find that the M11-L density functional has higher accuracy than CCSD(T)/CBS for the HC(O)F + CH₂OO and HC(O)F + anti-CH₃CHOO reactions. We find significant negative temperature dependence in the ratios of the rate constants for HC(O)F + CH₂OO/anti-CH₃CHOO to the rate constant for HC(O)F + OH. We also find that different Criegee intermediates have different rate-determining-steps in their reactions with formyl fluoride, and we find that the dominant gas-phase removal mechanism for HC(O)F in the atmosphere is the reaction with CH₂OO and/or anti-CH₃CHOO Criegee intermediates.

Original language	English (US)
Journal	Fundamental Research
DOIs	https://doi.org/10.1016/j.fmre.2023.02.012
State	Accepted/In press - 2023
Externally published	Yes

Bibliographical note

Funding Information:
This work was supported in part by the National Natural Science Foundation of China (42120104007 and 41775125), by Guizhou Provincial Science and Technology Projects, China (CXTD [2022]001), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China (KY[2021]014 and KY[2021]107). The work of DGT was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997. We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources.

Funding Information:
This work was supported in part by the National Natural Science Foundation of China ( 42120104007 and 41775125 ), by Guizhou Provincial Science and Technology Projects, China ( CXTD [2022]001 ), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China ( KY[2021]014 and KY[2021]107 ). The work of DGT was supported in part by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997 . We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources.

Publisher Copyright:
© 2023

Keywords

Atmospheric oxidation capacity
CCSDT(Q)/CBS calculations
Criegee intermediates
Formyl fluoride
Reaction kinetics

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10.1016/j.fmre.2023.02.012

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@article{003a9973ec754db48f0b651889f03a13,

title = "Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere",

abstract = "Atmospheric oxidation processes are of central importance in atmospheric climate models. It is often considered that volatile organic molecules are mainly removed by hydroxyl radical; however, the kinetics of some reactions of hydroxyl radical with volatile organic molecules are slow. Here we report rate constants for rapid reactions of formyl fluoride with Criegee intermediates. These rate constants are calculated by dual-level multistructural canonical variational transition state theory with small-curvature tunneling (DL-MS-CVT/SCT). The treatment contains beyond-CCSD(T) electronic structure calculations for transition state theory, and it employs validated density functional input for multistructural canonical variational transition state theory with small-curvature tunneling and for variable-reaction-coordinate variational transition state theory. We find that the M11-L density functional has higher accuracy than CCSD(T)/CBS for the HC(O)F + CH2OO and HC(O)F + anti-CH3CHOO reactions. We find significant negative temperature dependence in the ratios of the rate constants for HC(O)F + CH2OO/anti-CH3CHOO to the rate constant for HC(O)F + OH. We also find that different Criegee intermediates have different rate-determining-steps in their reactions with formyl fluoride, and we find that the dominant gas-phase removal mechanism for HC(O)F in the atmosphere is the reaction with CH2OO and/or anti-CH3CHOO Criegee intermediates.",

keywords = "Atmospheric oxidation capacity, CCSDT(Q)/CBS calculations, Criegee intermediates, Formyl fluoride, Reaction kinetics",

author = "Yu Xia and Bo Long and Ai Liu and Truhlar, {Donald G.}",

note = "Funding Information: This work was supported in part by the National Natural Science Foundation of China (42120104007 and 41775125), by Guizhou Provincial Science and Technology Projects, China (CXTD [2022]001), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China (KY[2021]014 and KY[2021]107). The work of DGT was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997. We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources. Funding Information: This work was supported in part by the National Natural Science Foundation of China ( 42120104007 and 41775125 ), by Guizhou Provincial Science and Technology Projects, China ( CXTD [2022]001 ), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China ( KY[2021]014 and KY[2021]107 ). The work of DGT was supported in part by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997 . We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources. Publisher Copyright: {\textcopyright} 2023",

year = "2023",

doi = "10.1016/j.fmre.2023.02.012",

language = "English (US)",

journal = "Fundamental Research",

issn = "2096-9457",

publisher = "Elsevier BV",

}

TY - JOUR

T1 - Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

AU - Xia, Yu

AU - Long, Bo

AU - Liu, Ai

AU - Truhlar, Donald G.

N1 - Funding Information: This work was supported in part by the National Natural Science Foundation of China (42120104007 and 41775125), by Guizhou Provincial Science and Technology Projects, China (CXTD [2022]001), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China (KY[2021]014 and KY[2021]107). The work of DGT was supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997. We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources. Funding Information: This work was supported in part by the National Natural Science Foundation of China ( 42120104007 and 41775125 ), by Guizhou Provincial Science and Technology Projects, China ( CXTD [2022]001 ), and by the Science and Technology Foundation of Guizhou Provincial Department of Education, China ( KY[2021]014 and KY[2021]107 ). The work of DGT was supported in part by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences under Award DE-SC0015997 . We also acknowledge the Minnesota Supercomputing Institute and the National Energy Research Scientific Computing Center for computational resources. Publisher Copyright: © 2023

PY - 2023

Y1 - 2023

N2 - Atmospheric oxidation processes are of central importance in atmospheric climate models. It is often considered that volatile organic molecules are mainly removed by hydroxyl radical; however, the kinetics of some reactions of hydroxyl radical with volatile organic molecules are slow. Here we report rate constants for rapid reactions of formyl fluoride with Criegee intermediates. These rate constants are calculated by dual-level multistructural canonical variational transition state theory with small-curvature tunneling (DL-MS-CVT/SCT). The treatment contains beyond-CCSD(T) electronic structure calculations for transition state theory, and it employs validated density functional input for multistructural canonical variational transition state theory with small-curvature tunneling and for variable-reaction-coordinate variational transition state theory. We find that the M11-L density functional has higher accuracy than CCSD(T)/CBS for the HC(O)F + CH2OO and HC(O)F + anti-CH3CHOO reactions. We find significant negative temperature dependence in the ratios of the rate constants for HC(O)F + CH2OO/anti-CH3CHOO to the rate constant for HC(O)F + OH. We also find that different Criegee intermediates have different rate-determining-steps in their reactions with formyl fluoride, and we find that the dominant gas-phase removal mechanism for HC(O)F in the atmosphere is the reaction with CH2OO and/or anti-CH3CHOO Criegee intermediates.

AB - Atmospheric oxidation processes are of central importance in atmospheric climate models. It is often considered that volatile organic molecules are mainly removed by hydroxyl radical; however, the kinetics of some reactions of hydroxyl radical with volatile organic molecules are slow. Here we report rate constants for rapid reactions of formyl fluoride with Criegee intermediates. These rate constants are calculated by dual-level multistructural canonical variational transition state theory with small-curvature tunneling (DL-MS-CVT/SCT). The treatment contains beyond-CCSD(T) electronic structure calculations for transition state theory, and it employs validated density functional input for multistructural canonical variational transition state theory with small-curvature tunneling and for variable-reaction-coordinate variational transition state theory. We find that the M11-L density functional has higher accuracy than CCSD(T)/CBS for the HC(O)F + CH2OO and HC(O)F + anti-CH3CHOO reactions. We find significant negative temperature dependence in the ratios of the rate constants for HC(O)F + CH2OO/anti-CH3CHOO to the rate constant for HC(O)F + OH. We also find that different Criegee intermediates have different rate-determining-steps in their reactions with formyl fluoride, and we find that the dominant gas-phase removal mechanism for HC(O)F in the atmosphere is the reaction with CH2OO and/or anti-CH3CHOO Criegee intermediates.

KW - Atmospheric oxidation capacity

KW - CCSDT(Q)/CBS calculations

KW - Criegee intermediates

KW - Formyl fluoride

KW - Reaction kinetics

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U2 - 10.1016/j.fmre.2023.02.012

DO - 10.1016/j.fmre.2023.02.012

M3 - Article

AN - SCOPUS:85151400748

SN - 2096-9457

JO - Fundamental Research

JF - Fundamental Research

ER -

Reactions with criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

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