Dissociation of the ethyl formate radical cation: A computational mechanistic study

Joong Chul Choe; Myung Hwa Kim

doi:10.1016/j.cplett.2019.06.055

Dissociation of the ethyl formate radical cation: A computational mechanistic study

Joong Chul Choe, Myung Hwa Kim

Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

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Abstract

We report a theoretical study of unimolecular dissociation of the ethyl formate radical cation (C₂H₅OCHO^+[rad]). The potential energy surface (PES) of its 14 dissociation reactions, including the formation of CH₂CHC(OH)₂⁺, CH₂CH₂CO^+[rad], CH₃CHCO^+[rad], CH₂OCHO⁺, HOCHOH⁺, HOCO⁺, CH₃CHOH⁺, HCO₂⁺, CH₂OH⁺, C₂H₆^+[rad], C₂H₅⁺, HCO⁺, and C₂H₄^+[rad], was determined using G4 calculation. A kinetic analysis using RRKM calculations based on the PES obtained adequately explained the results of previous experiments, suggesting that the dissociation occurred statistically from the electronic ground state.

Original language	English
Pages (from-to)	538-543
Number of pages	6
Journal	Chemical Physics Letters
Volume	730
DOIs	https://doi.org/10.1016/j.cplett.2019.06.055
State	Published - Sep 2019

Bibliographical note

Funding Information:
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2018R1A6A1A03025340 for K.M.H).

Publisher Copyright:
© 2019 Elsevier B.V.

Keywords

G4 calculation
Kinetics
Mechanism
RRKM calculation

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10.1016/j.cplett.2019.06.055

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title = "Dissociation of the ethyl formate radical cation: A computational mechanistic study",

abstract = "We report a theoretical study of unimolecular dissociation of the ethyl formate radical cation (C2H5OCHO+[rad]). The potential energy surface (PES) of its 14 dissociation reactions, including the formation of CH2CHC(OH)2+, CH2CH2CO+[rad], CH3CHCO+[rad], CH2OCHO+, HOCHOH+, HOCO+, CH3CHOH+, HCO2+, CH2OH+, C2H6+[rad], C2H5+, HCO+, and C2H4+[rad], was determined using G4 calculation. A kinetic analysis using RRKM calculations based on the PES obtained adequately explained the results of previous experiments, suggesting that the dissociation occurred statistically from the electronic ground state.",

keywords = "G4 calculation, Kinetics, Mechanism, RRKM calculation",

author = "Choe, {Joong Chul} and Kim, {Myung Hwa}",

note = "Funding Information: This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2018R1A6A1A03025340 for K.M.H). Publisher Copyright: {\textcopyright} 2019 Elsevier B.V.",

year = "2019",

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doi = "10.1016/j.cplett.2019.06.055",

language = "English",

volume = "730",

pages = "538--543",

journal = "Chemical Physics Letters",

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T1 - Dissociation of the ethyl formate radical cation

T2 - A computational mechanistic study

AU - Choe, Joong Chul

AU - Kim, Myung Hwa

N1 - Funding Information: This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2018R1A6A1A03025340 for K.M.H). Publisher Copyright: © 2019 Elsevier B.V.

PY - 2019/9

Y1 - 2019/9

N2 - We report a theoretical study of unimolecular dissociation of the ethyl formate radical cation (C2H5OCHO+[rad]). The potential energy surface (PES) of its 14 dissociation reactions, including the formation of CH2CHC(OH)2+, CH2CH2CO+[rad], CH3CHCO+[rad], CH2OCHO+, HOCHOH+, HOCO+, CH3CHOH+, HCO2+, CH2OH+, C2H6+[rad], C2H5+, HCO+, and C2H4+[rad], was determined using G4 calculation. A kinetic analysis using RRKM calculations based on the PES obtained adequately explained the results of previous experiments, suggesting that the dissociation occurred statistically from the electronic ground state.

AB - We report a theoretical study of unimolecular dissociation of the ethyl formate radical cation (C2H5OCHO+[rad]). The potential energy surface (PES) of its 14 dissociation reactions, including the formation of CH2CHC(OH)2+, CH2CH2CO+[rad], CH3CHCO+[rad], CH2OCHO+, HOCHOH+, HOCO+, CH3CHOH+, HCO2+, CH2OH+, C2H6+[rad], C2H5+, HCO+, and C2H4+[rad], was determined using G4 calculation. A kinetic analysis using RRKM calculations based on the PES obtained adequately explained the results of previous experiments, suggesting that the dissociation occurred statistically from the electronic ground state.

KW - G4 calculation

KW - Kinetics

KW - Mechanism

KW - RRKM calculation

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U2 - 10.1016/j.cplett.2019.06.055

DO - 10.1016/j.cplett.2019.06.055

M3 - Article

AN - SCOPUS:85067831429

SN - 0009-2614

VL - 730

SP - 538

EP - 543

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Dissociation of the ethyl formate radical cation: A computational mechanistic study

Abstract

Bibliographical note

Keywords

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