Resolving the mystery of prompt CO{sub 2} : the HCCO + 0{sub 2} reaction.

PDF Version Also Available for Download.

Description

The reaction of methyl radicals with hydrogen atoms is studied with a combination of ab initio quantum chemistry, variational transition state theory, and classical trajectory simulations. The interaction between the two radicals, including the umbrella mode of the methyl radical, is examined at the CAS+1+2 level using an augmented correlation consistent polarized valence triple zeta basis set. The implementation of an analytic representation of the ab initio data within variable reaction coordinate transition state theory yields predictions for the zero-pressure limit isotopic exchange rate constants that are about 15% greater than the available experimental data. Trajectory simulations indicate that the ... continued below

Physical Description

vp.

Creation Information

Klippenstein, S.; Miller, J. & Harding, L. December 13, 2001.

Context

This article is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this article can be viewed below.

Who

People and organizations associated with either the creation of this article or its content.

Sponsor

Publisher

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this article. Follow the links below to find similar items on the Digital Library.

Description

The reaction of methyl radicals with hydrogen atoms is studied with a combination of ab initio quantum chemistry, variational transition state theory, and classical trajectory simulations. The interaction between the two radicals, including the umbrella mode of the methyl radical, is examined at the CAS+1+2 level using an augmented correlation consistent polarized valence triple zeta basis set. The implementation of an analytic representation of the ab initio data within variable reaction coordinate transition state theory yields predictions for the zero-pressure limit isotopic exchange rate constants that are about 15% greater than the available experimental data. Trajectory simulations indicate that the transition state recrossing factor for the capture process is 0.90, essentially independent of temperature and isotope. The dynamically corrected theoretical prediction for the CH{sub 3} + H high pressure rate coefficient is well reproduced by the expression 1.32 x 10{sup -10}T{sup 0.153}exp(-15.1/RT) cm{sup 3}molecule{sup -1}s{sup -1}, where R = 1.987 cal mole{sup -1} K{sup -1}, for temperatures between 200 and 2400 K. This prediction is in good agreement with the converted experimental data for all but the one measurement at 200 K. Calculations for the triplet abstraction channel suggest that it is unimportant. Methyl umbrella mode variations have surprisingly little effect on the predicted rate coefficients.

Physical Description

vp.

Source

  • 29th International Symposium on Combustion, Sapporo (JP), 07/21/2002--07/26/2002

Language

Item Type

Identifier

Unique identifying numbers for this article in the Digital Library or other systems.

  • Report No.: ANL/CHM/CP-106435
  • Grant Number: W-31-109-ENG-38
  • Office of Scientific & Technical Information Report Number: 799818
  • Archival Resource Key: ark:/67531/metadc743166

Collections

This article is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

Office of Scientific and Technical Information (OSTI) is the Department of Energy (DOE) office that collects, preserves, and disseminates DOE-sponsored research and development (R&D) results that are the outcomes of R&D projects or other funded activities at DOE labs and facilities nationwide and grantees at universities and other institutions.

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • December 13, 2001

Added to The UNT Digital Library

  • Oct. 19, 2015, 7:39 p.m.

Description Last Updated

  • March 29, 2016, 9:07 p.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 2

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Klippenstein, S.; Miller, J. & Harding, L. Resolving the mystery of prompt CO{sub 2} : the HCCO + 0{sub 2} reaction., article, December 13, 2001; Illinois. (digital.library.unt.edu/ark:/67531/metadc743166/: accessed December 13, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.