Abstract.
The advent of computer-aided methods for constructing detailed kinetic models of multicomponent reacting systems provides fresh motivation for the development of efficient and accurate methods for estimating rate constants. There is now the real likelihood that a priori rate estimates, formerly of primarily academic interest, could directly impact major public policy and business decisions. This opportunity brings many challenges. The process of building a computer model for a real-world system can require hundreds of thousands of rate estimates, making most existing rate calculation techniques impractical. Also, the demands for tight error bars on model predictions used to make major decisions often imply levels of accuracy unachievable with existing rate calculation techniques. Past and recent progress towards developing fast and accurate rate estimates is selectively reviewed, and our methodology is outlined. New rate estimates for several types of reactions involving O and HO2 are presented. Several technical issues requiring further work by the theoretical chemistry community are highlighted. Electronic supplementary material to this paper can be obtained by using the Springer Link server located at http://dx.doi.org/10.1007/s00214-002-0368-4.
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Received: 6 February 2002 / Accepted: 2 June 2002 / Published online: 2 October 2002
Acknowledgements. This work was partially supported by the National Computational Science Alliance under Grant CTS010006 N and utilized the Origin 2000 High-performance Computing and UniTree Mass Storage systems. We are grateful for financial support from the EPA Center for Airborne Organics, the NSF CAREER program, Alstom Power, Dow Chemical, and the Office of Basic Energy Science, U.S. Department of Energy through grant DE-FG02-98ER14914. The authors acknowledge the contribution of Hans-Heinrich Carstensen in the initial stages of this work.
Correspondence to: W.H. Green Jr. e-mail: whgreen@mit.edu
Electronic supplementary material to this paper can be obtained by using the Springer LINK server located at http://dx.doi.org/10.1007/s00214-002-0368-4
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Sumathi, R., Green Jr., W. A priori rate constants for kinetic modeling. Theor Chem Acc 108, 187–213 (2002). https://doi.org/10.1007/s00214-002-0368-4
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DOI: https://doi.org/10.1007/s00214-002-0368-4