Automatic estimation of pressure-dependent rate coefficients

Handle URI:
http://hdl.handle.net/10754/597639
Title:
Automatic estimation of pressure-dependent rate coefficients
Authors:
Allen, Joshua W.; Goldsmith, C. Franklin; Green, William H.
Abstract:
A general framework is presented for accurately and efficiently estimating the phenomenological pressure-dependent rate coefficients for reaction networks of arbitrary size and complexity using only high-pressure-limit information. Two aspects of this framework are discussed in detail. First, two methods of estimating the density of states of the species in the network are presented, including a new method based on characteristic functional group frequencies. Second, three methods of simplifying the full master equation model of the network to a single set of phenomenological rates are discussed, including a new method based on the reservoir state and pseudo-steady state approximations. Both sets of methods are evaluated in the context of the chemically-activated reaction of acetyl with oxygen. All three simplifications of the master equation are usually accurate, but each fails in certain situations, which are discussed. The new methods usually provide good accuracy at a computational cost appropriate for automated reaction mechanism generation. This journal is © the Owner Societies.
Citation:
Allen JW, Goldsmith CF, Green WH (2012) Automatic estimation of pressure-dependent rate coefficients. Phys Chem Chem Phys 14: 1131–1155. Available: http://dx.doi.org/10.1039/c1cp22765c.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Phys. Chem. Chem. Phys.
KAUST Grant Number:
KUS-I1-010-01
Issue Date:
2012
DOI:
10.1039/c1cp22765c
PubMed ID:
22146884
Type:
Article
ISSN:
1463-9076; 1463-9084
Sponsors:
This work was funded in part by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DEFG02-98ER14914.; and by Award No. KUS-I1-010-01, made by King Abdullah University of Science and Technology (KAUST). Their financial support is gratefully acknowledged.
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Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorAllen, Joshua W.en
dc.contributor.authorGoldsmith, C. Franklinen
dc.contributor.authorGreen, William H.en
dc.date.accessioned2016-02-25T12:43:32Zen
dc.date.available2016-02-25T12:43:32Zen
dc.date.issued2012en
dc.identifier.citationAllen JW, Goldsmith CF, Green WH (2012) Automatic estimation of pressure-dependent rate coefficients. Phys Chem Chem Phys 14: 1131–1155. Available: http://dx.doi.org/10.1039/c1cp22765c.en
dc.identifier.issn1463-9076en
dc.identifier.issn1463-9084en
dc.identifier.pmid22146884en
dc.identifier.doi10.1039/c1cp22765cen
dc.identifier.urihttp://hdl.handle.net/10754/597639en
dc.description.abstractA general framework is presented for accurately and efficiently estimating the phenomenological pressure-dependent rate coefficients for reaction networks of arbitrary size and complexity using only high-pressure-limit information. Two aspects of this framework are discussed in detail. First, two methods of estimating the density of states of the species in the network are presented, including a new method based on characteristic functional group frequencies. Second, three methods of simplifying the full master equation model of the network to a single set of phenomenological rates are discussed, including a new method based on the reservoir state and pseudo-steady state approximations. Both sets of methods are evaluated in the context of the chemically-activated reaction of acetyl with oxygen. All three simplifications of the master equation are usually accurate, but each fails in certain situations, which are discussed. The new methods usually provide good accuracy at a computational cost appropriate for automated reaction mechanism generation. This journal is © the Owner Societies.en
dc.description.sponsorshipThis work was funded in part by the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DEFG02-98ER14914.; and by Award No. KUS-I1-010-01, made by King Abdullah University of Science and Technology (KAUST). Their financial support is gratefully acknowledged.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.titleAutomatic estimation of pressure-dependent rate coefficientsen
dc.typeArticleen
dc.identifier.journalPhys. Chem. Chem. Phys.en
dc.contributor.institutionMassachusetts Institute of Technology, Cambridge, United Statesen
dc.contributor.institutionFritz Haber Institute of the Max Planck Society, Berlin, Germanyen
kaust.grant.numberKUS-I1-010-01en
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