Ab initio kinetics for the decomposition of hydroxybutyl and butoxy radicals of n-butanol

Peng Zhang; Stephen J. Klippenstein; Chung K. Law

doi:10.1021/jp400155z

Ab initio kinetics for the decomposition of hydroxybutyl and butoxy radicals of n-butanol

Peng Zhang
, Stephen J. Klippenstein
, Chung K. Law

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

88 Citations (Scopus)

Abstract

The decomposition kinetics of the hydroxybutyl and butoxy radicals (C ₄H₉O) arising via H abstraction from n-butanol were studied theoretically with ab initio transition-state-theory-based master equation analyses. Stationary points on the C₄H₉O potential energy surface were calculated at either the RQCISD(T)/CBS//B3LYP/6- 311++G(d,p) level or the RQCISD(T)/CBS//CASPT2/aug-cc-pVDZ level. Unimolecular pressure- and temperature-dependent rate coefficients were calculated over broad ranges of temperature (300-2500 K) and pressure (1.3 × 10^-3 to 10² atm) by solving the time-dependent multiple-well master equation. The "well merging" phenomenon was observed and analyzed for its influence on the branching ratios and rate coefficients. The theoretical predictions were compared with the available experimental and theoretical data and any discrepancies were analyzed. The predicted rate coefficients are represented with forms that may readily be used in combustion modeling of n-butanol. © 2013 American Chemical Society.

Original language	English
Pages (from-to)	1890-1906
Journal	The Journal of Physical Chemistry A
Volume	117
Issue number	9
DOIs	https://doi.org/10.1021/jp400155z
Publication status	Published - 7 Mar 2013
Externally published	Yes

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Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

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title = "Ab initio kinetics for the decomposition of hydroxybutyl and butoxy radicals of n-butanol",

abstract = "The decomposition kinetics of the hydroxybutyl and butoxy radicals (C 4H9O) arising via H abstraction from n-butanol were studied theoretically with ab initio transition-state-theory-based master equation analyses. Stationary points on the C4H9O potential energy surface were calculated at either the RQCISD(T)/CBS//B3LYP/6- 311++G(d,p) level or the RQCISD(T)/CBS//CASPT2/aug-cc-pVDZ level. Unimolecular pressure- and temperature-dependent rate coefficients were calculated over broad ranges of temperature (300-2500 K) and pressure (1.3 × 10-3 to 102 atm) by solving the time-dependent multiple-well master equation. The {"}well merging{"} phenomenon was observed and analyzed for its influence on the branching ratios and rate coefficients. The theoretical predictions were compared with the available experimental and theoretical data and any discrepancies were analyzed. The predicted rate coefficients are represented with forms that may readily be used in combustion modeling of n-butanol. {\textcopyright} 2013 American Chemical Society.",

author = "Peng Zhang and Klippenstein, \{Stephen J.\} and Law, \{Chung K.\}",

note = "Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].",

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T1 - Ab initio kinetics for the decomposition of hydroxybutyl and butoxy radicals of n-butanol

AU - Zhang, Peng

AU - Klippenstein, Stephen J.

AU - Law, Chung K.

N1 - Publication details (e.g. title, author(s), publication statuses and dates) are captured on an “AS IS” and “AS AVAILABLE” basis at the time of record harvesting from the data source. Suggestions for further amendments or supplementary information can be sent to [email protected].

PY - 2013/3/7

Y1 - 2013/3/7

N2 - The decomposition kinetics of the hydroxybutyl and butoxy radicals (C 4H9O) arising via H abstraction from n-butanol were studied theoretically with ab initio transition-state-theory-based master equation analyses. Stationary points on the C4H9O potential energy surface were calculated at either the RQCISD(T)/CBS//B3LYP/6- 311++G(d,p) level or the RQCISD(T)/CBS//CASPT2/aug-cc-pVDZ level. Unimolecular pressure- and temperature-dependent rate coefficients were calculated over broad ranges of temperature (300-2500 K) and pressure (1.3 × 10-3 to 102 atm) by solving the time-dependent multiple-well master equation. The "well merging" phenomenon was observed and analyzed for its influence on the branching ratios and rate coefficients. The theoretical predictions were compared with the available experimental and theoretical data and any discrepancies were analyzed. The predicted rate coefficients are represented with forms that may readily be used in combustion modeling of n-butanol. © 2013 American Chemical Society.

AB - The decomposition kinetics of the hydroxybutyl and butoxy radicals (C 4H9O) arising via H abstraction from n-butanol were studied theoretically with ab initio transition-state-theory-based master equation analyses. Stationary points on the C4H9O potential energy surface were calculated at either the RQCISD(T)/CBS//B3LYP/6- 311++G(d,p) level or the RQCISD(T)/CBS//CASPT2/aug-cc-pVDZ level. Unimolecular pressure- and temperature-dependent rate coefficients were calculated over broad ranges of temperature (300-2500 K) and pressure (1.3 × 10-3 to 102 atm) by solving the time-dependent multiple-well master equation. The "well merging" phenomenon was observed and analyzed for its influence on the branching ratios and rate coefficients. The theoretical predictions were compared with the available experimental and theoretical data and any discrepancies were analyzed. The predicted rate coefficients are represented with forms that may readily be used in combustion modeling of n-butanol. © 2013 American Chemical Society.

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UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84874832319&origin=recordpage

U2 - 10.1021/jp400155z

DO - 10.1021/jp400155z

M3 - RGC 21 - Publication in refereed journal

C2 - 23394217

SN - 1089-5639

VL - 117

SP - 1890

EP - 1906

JO - The Journal of Physical Chemistry A

JF - The Journal of Physical Chemistry A

IS - 9

ER -

Ab initio kinetics for the decomposition of hydroxybutyl and butoxy radicals of n-butanol

Abstract

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