A 135-theoretical study on the potential energy surface of the NCS+NO 2 reaction

Zhi Gang Wei; Xu Ri Huang; Yan Bo Sun; Shao Wen Zhang; Chia Chung Sun

doi:10.1016/j.theochem.2004.07.018

A 135-theoretical study on the potential energy surface of the NCS+NO ₂ reaction

Zhi Gang Wei
, Xu Ri Huang
, Yan Bo Sun
, Shao Wen Zhang
, Chia Chung Sun

School of Chemistry and Chemical Engineering

Jilin University

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

2 Citations (Scopus)

Abstract

In the present study, the reaction mechanism of NCS+NO ₂ on the singlet potential energy surface is studied using the MP2/6-311G(d,p) level of theory. It is shown that the pathway (1) NCS+NO2O(O)NNCS→O(NNC(S)O) →N2O+OCS is the major pathway, and the pathways (2) NCS+NO2O(O) NSCN→ONS+OCN and (3) NCS+NO2ciscisONONCS→NO+SCNO are the minor pathways in the singlet potential energy surface. The major pathway (1), involving the barrierless entrance to the first adduct isomer O(O)NNCS and tight transition states to the products N ₂O and OCS, is in good agreement with the experimentally observed negative temperature dependence of rate constants. The energies of the stationary points are refined using a multi-level method.

Original language	English
Pages (from-to)	135-139
Number of pages	5
Journal	Journal of Molecular Structure: THEOCHEM
Volume	684
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2004.07.018
Publication status	Published - 27 Sept 2004

Keywords

Isomers
Mechanism
Potential energy surface

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10.1016/j.theochem.2004.07.018

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title = "A 135-theoretical study on the potential energy surface of the NCS+NO 2 reaction",

abstract = "In the present study, the reaction mechanism of NCS+NO 2 on the singlet potential energy surface is studied using the MP2/6-311G(d,p) level of theory. It is shown that the pathway (1) NCS+NO2O(O)NNCS→O(NNC(S)O) →N2O+OCS is the major pathway, and the pathways (2) NCS+NO2O(O) NSCN→ONS+OCN and (3) NCS+NO2ciscisONONCS→NO+SCNO are the minor pathways in the singlet potential energy surface. The major pathway (1), involving the barrierless entrance to the first adduct isomer O(O)NNCS and tight transition states to the products N 2O and OCS, is in good agreement with the experimentally observed negative temperature dependence of rate constants. The energies of the stationary points are refined using a multi-level method.",

keywords = "Isomers, Mechanism, Potential energy surface",

author = "Wei, \{Zhi Gang\} and Huang, \{Xu Ri\} and Sun, \{Yan Bo\} and Zhang, \{Shao Wen\} and Sun, \{Chia Chung\}",

year = "2004",

month = sep,

day = "27",

doi = "10.1016/j.theochem.2004.07.018",

language = "English",

volume = "684",

pages = "135--139",

journal = "Journal of Molecular Structure: THEOCHEM",

issn = "0166-1280",

publisher = "Elsevier B.V.",

number = "1-3",

}

TY - JOUR

T1 - A 135-theoretical study on the potential energy surface of the NCS+NO 2 reaction

AU - Wei, Zhi Gang

AU - Huang, Xu Ri

AU - Sun, Yan Bo

AU - Zhang, Shao Wen

AU - Sun, Chia Chung

PY - 2004/9/27

Y1 - 2004/9/27

N2 - In the present study, the reaction mechanism of NCS+NO 2 on the singlet potential energy surface is studied using the MP2/6-311G(d,p) level of theory. It is shown that the pathway (1) NCS+NO2O(O)NNCS→O(NNC(S)O) →N2O+OCS is the major pathway, and the pathways (2) NCS+NO2O(O) NSCN→ONS+OCN and (3) NCS+NO2ciscisONONCS→NO+SCNO are the minor pathways in the singlet potential energy surface. The major pathway (1), involving the barrierless entrance to the first adduct isomer O(O)NNCS and tight transition states to the products N 2O and OCS, is in good agreement with the experimentally observed negative temperature dependence of rate constants. The energies of the stationary points are refined using a multi-level method.

AB - In the present study, the reaction mechanism of NCS+NO 2 on the singlet potential energy surface is studied using the MP2/6-311G(d,p) level of theory. It is shown that the pathway (1) NCS+NO2O(O)NNCS→O(NNC(S)O) →N2O+OCS is the major pathway, and the pathways (2) NCS+NO2O(O) NSCN→ONS+OCN and (3) NCS+NO2ciscisONONCS→NO+SCNO are the minor pathways in the singlet potential energy surface. The major pathway (1), involving the barrierless entrance to the first adduct isomer O(O)NNCS and tight transition states to the products N 2O and OCS, is in good agreement with the experimentally observed negative temperature dependence of rate constants. The energies of the stationary points are refined using a multi-level method.

KW - Isomers

KW - Mechanism

KW - Potential energy surface

UR - https://www.scopus.com/pages/publications/5444274726

U2 - 10.1016/j.theochem.2004.07.018

DO - 10.1016/j.theochem.2004.07.018

M3 - Article

AN - SCOPUS:5444274726

SN - 0166-1280

VL - 684

SP - 135

EP - 139

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

A 135-theoretical study on the potential energy surface of the NCS+NO ₂ reaction

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Keywords

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