Theoretical investigation on the gas phase thermolysis mechanism and rate constant of diacetamide

Shao Wen Zhang; Yan Wang; Wen Lin Feng

doi:10.1016/S0166-1280(98)00603-4

Theoretical investigation on the gas phase thermolysis mechanism and rate constant of diacetamide

Shao Wen Zhang
, Yan Wang^*
, Wen Lin Feng

^*Corresponding author for this work

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

7 Citations (Scopus)

Abstract

The gas-phase thermolysis mechanism of diacetamide (CH₃C(O)NHC(O)CH₃) was investigated using ab initio method at HF/6-31G (d,p) level, Moler- Plesset method at MP2/6-31G (d,p) level and hybrid density functional theory (DFT) at B3LYP/6-31G (d,p) level. It was found that Hartree-Fock method is not suitable to predict the mechanism for this reaction. A semiconcerted mechanism with a six-membered cyclic transition state was found at MP2/6-31G (d,p) and B3LYP/6-31G (d,p) levels of theory. The refined barrier at B3LYP/6- 311+G [df, p) level of theory is about 179.50 kJ mol^-1 with the Zero-Point- Vibrational-Energy (ZPVE) correction; Microcanonical transition state theory was used to calculate rate constants for the reaction. The calculated rate constants are in good agreement with experimental values.

Original language	English
Pages (from-to)	29-35
Number of pages	7
Journal	Journal of Molecular Structure: THEOCHEM
Volume	488
Issue number	1-3
DOIs	https://doi.org/10.1016/S0166-1280(98)00603-4
Publication status	Published - 1 Oct 1999
Externally published	Yes

Keywords

Calculation
Density functional theory
Diacetamide
Rate constants
Thermolysis mechanism

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10.1016/S0166-1280(98)00603-4

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title = "Theoretical investigation on the gas phase thermolysis mechanism and rate constant of diacetamide",

abstract = "The gas-phase thermolysis mechanism of diacetamide (CH3C(O)NHC(O)CH3) was investigated using ab initio method at HF/6-31G (d,p) level, Moler- Plesset method at MP2/6-31G (d,p) level and hybrid density functional theory (DFT) at B3LYP/6-31G (d,p) level. It was found that Hartree-Fock method is not suitable to predict the mechanism for this reaction. A semiconcerted mechanism with a six-membered cyclic transition state was found at MP2/6-31G (d,p) and B3LYP/6-31G (d,p) levels of theory. The refined barrier at B3LYP/6- 311+G [df, p) level of theory is about 179.50 kJ mol-1 with the Zero-Point- Vibrational-Energy (ZPVE) correction; Microcanonical transition state theory was used to calculate rate constants for the reaction. The calculated rate constants are in good agreement with experimental values.",

keywords = "Calculation, Density functional theory, Diacetamide, Rate constants, Thermolysis mechanism",

author = "Zhang, \{Shao Wen\} and Yan Wang and Feng, \{Wen Lin\}",

year = "1999",

month = oct,

day = "1",

doi = "10.1016/S0166-1280(98)00603-4",

language = "English",

volume = "488",

pages = "29--35",

journal = "Journal of Molecular Structure: THEOCHEM",

issn = "0166-1280",

publisher = "Elsevier B.V.",

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TY - JOUR

T1 - Theoretical investigation on the gas phase thermolysis mechanism and rate constant of diacetamide

AU - Zhang, Shao Wen

AU - Wang, Yan

AU - Feng, Wen Lin

PY - 1999/10/1

Y1 - 1999/10/1

N2 - The gas-phase thermolysis mechanism of diacetamide (CH3C(O)NHC(O)CH3) was investigated using ab initio method at HF/6-31G (d,p) level, Moler- Plesset method at MP2/6-31G (d,p) level and hybrid density functional theory (DFT) at B3LYP/6-31G (d,p) level. It was found that Hartree-Fock method is not suitable to predict the mechanism for this reaction. A semiconcerted mechanism with a six-membered cyclic transition state was found at MP2/6-31G (d,p) and B3LYP/6-31G (d,p) levels of theory. The refined barrier at B3LYP/6- 311+G [df, p) level of theory is about 179.50 kJ mol-1 with the Zero-Point- Vibrational-Energy (ZPVE) correction; Microcanonical transition state theory was used to calculate rate constants for the reaction. The calculated rate constants are in good agreement with experimental values.

AB - The gas-phase thermolysis mechanism of diacetamide (CH3C(O)NHC(O)CH3) was investigated using ab initio method at HF/6-31G (d,p) level, Moler- Plesset method at MP2/6-31G (d,p) level and hybrid density functional theory (DFT) at B3LYP/6-31G (d,p) level. It was found that Hartree-Fock method is not suitable to predict the mechanism for this reaction. A semiconcerted mechanism with a six-membered cyclic transition state was found at MP2/6-31G (d,p) and B3LYP/6-31G (d,p) levels of theory. The refined barrier at B3LYP/6- 311+G [df, p) level of theory is about 179.50 kJ mol-1 with the Zero-Point- Vibrational-Energy (ZPVE) correction; Microcanonical transition state theory was used to calculate rate constants for the reaction. The calculated rate constants are in good agreement with experimental values.

KW - Calculation

KW - Density functional theory

KW - Diacetamide

KW - Rate constants

KW - Thermolysis mechanism

UR - https://www.scopus.com/pages/publications/0033214392

U2 - 10.1016/S0166-1280(98)00603-4

DO - 10.1016/S0166-1280(98)00603-4

M3 - Article

AN - SCOPUS:0033214392

SN - 0166-1280

VL - 488

SP - 29

EP - 35

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Theoretical investigation on the gas phase thermolysis mechanism and rate constant of diacetamide

Abstract

Keywords

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