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Direct ab initio study on the rate constants of radical C-2(A(3)Pi(u))+C3H8 reaction

Huo, Rui-Ping ; Zhang, Xiang ; Huang, Xu-Ri ; Li, Jilai LU and Sun, Chia-Chung (2013) In Journal of Molecular Modeling 19(3). p.1009-1018
Abstract
The mechanism and kinetics of the radical C-3(2) + C3H8 reaction have been investigated theoretically by direct ab initio kinetics over a wide temperature range. The potential energy surfaces have been constructed at the CCSD(T)/B3//UMP2/B1 levels of theory. The electron transfer was also analyzed by quasi-restricted orbital (QRO) in detail. It was shown that all these channels proceed exclusively via hydrogen abstraction. The overall ICVT/SCT rate constants are in agreement with the available experimental results. The prediction shows that the secondary hydrogen of C3H8 abstraction by C-3(2) radical is the major pathway at low temperatures (below 700 K), while as the temperature increases, the primary hydrogen of C3H8 abstraction becomes... (More)
The mechanism and kinetics of the radical C-3(2) + C3H8 reaction have been investigated theoretically by direct ab initio kinetics over a wide temperature range. The potential energy surfaces have been constructed at the CCSD(T)/B3//UMP2/B1 levels of theory. The electron transfer was also analyzed by quasi-restricted orbital (QRO) in detail. It was shown that all these channels proceed exclusively via hydrogen abstraction. The overall ICVT/SCT rate constants are in agreement with the available experimental results. The prediction shows that the secondary hydrogen of C3H8 abstraction by C-3(2) radical is the major pathway at low temperatures (below 700 K), while as the temperature increases, the primary hydrogen of C3H8 abstraction becomes more important and more favorable. A negative temperature dependence of the rate constants for the reaction of C-3(2) + C3H8 was observed. The three-(k (3)) and four-parameter (k (4)) rate-temperature expressions were also provided within 243-2000 K to facilitate future experimental studies. (Less)
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author
; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
C-2, Chemical kinetics, Rate constant, Variational transition-state, theory
in
Journal of Molecular Modeling
volume
19
issue
3
pages
1009 - 1018
publisher
Springer
external identifiers
  • wos:000315349800005
  • scopus:84877148784
  • pmid:23108701
ISSN
1610-2940
DOI
10.1007/s00894-012-1616-8
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
29be1532-b9b4-4a16-9c4b-3cd936fa3a32 (old id 3670077)
date added to LUP
2016-04-01 09:53:47
date last changed
2023-01-01 23:09:47
@article{29be1532-b9b4-4a16-9c4b-3cd936fa3a32,
  abstract     = {{The mechanism and kinetics of the radical C-3(2) + C3H8 reaction have been investigated theoretically by direct ab initio kinetics over a wide temperature range. The potential energy surfaces have been constructed at the CCSD(T)/B3//UMP2/B1 levels of theory. The electron transfer was also analyzed by quasi-restricted orbital (QRO) in detail. It was shown that all these channels proceed exclusively via hydrogen abstraction. The overall ICVT/SCT rate constants are in agreement with the available experimental results. The prediction shows that the secondary hydrogen of C3H8 abstraction by C-3(2) radical is the major pathway at low temperatures (below 700 K), while as the temperature increases, the primary hydrogen of C3H8 abstraction becomes more important and more favorable. A negative temperature dependence of the rate constants for the reaction of C-3(2) + C3H8 was observed. The three-(k (3)) and four-parameter (k (4)) rate-temperature expressions were also provided within 243-2000 K to facilitate future experimental studies.}},
  author       = {{Huo, Rui-Ping and Zhang, Xiang and Huang, Xu-Ri and Li, Jilai and Sun, Chia-Chung}},
  issn         = {{1610-2940}},
  keywords     = {{C-2; Chemical kinetics; Rate constant; Variational transition-state; theory}},
  language     = {{eng}},
  number       = {{3}},
  pages        = {{1009--1018}},
  publisher    = {{Springer}},
  series       = {{Journal of Molecular Modeling}},
  title        = {{Direct ab initio study on the rate constants of radical C-2(A(3)Pi(u))+C3H8 reaction}},
  url          = {{http://dx.doi.org/10.1007/s00894-012-1616-8}},
  doi          = {{10.1007/s00894-012-1616-8}},
  volume       = {{19}},
  year         = {{2013}},
}