Kinetics and mechanistic detail of Ni⁺ assisted organic decomposition reaction at low internal energies.

Laboren, Ivanna E.

Kinetics and mechanistic detail of Ni⁺ assisted organic decomposition reaction at low internal energies.

dc.contributor.advisor	Bellert, Darrin Joseph, 1968-
dc.contributor.author	Laboren, Ivanna E.
dc.contributor.department	Chemistry and Biochemistry.	en_US
dc.contributor.schools	Baylor University. Dept. of Chemistry and Biochemistry.	en_US
dc.date.accessioned	2011-12-19T19:53:25Z
dc.date.available	2011-12-19T19:53:25Z
dc.date.copyright	2011-12
dc.date.issued	2011-12-19
dc.description.abstract	The unimolecular decomposition kinetics of jet-cooled cluster ions have been monitored over ranges of internal energies. The clusters are formed by the combination of Ni cation with and organic ketone, aldehyde or ether molecules. The internal energy delivered to the clusters is provided through laser photon absorption. The quantum of photon energy approximates the total energy content of the reacting species as the clusters are jet cooled prior to photon absorption. The interaction of the organic substrate with the transition metal cation lowers the kinetic barriers to the activation of σ-bond. Thus the cation activates organic bonds and mediates the formation of products. The unimolecular decomposition products in these studies are a stable neutral with the corresponding ion. This dissertation will focus on the unimolecular decomposition kinetics of Ni⁺- Butanone. First order rate constants are acquired for the precursor ion dissociation into three product channels. The temporal growth of each fragment ion is selectively monitored and yields similar valued rate constants. The common-valued rate constants, comparisons to earlier studies, and the results of DFT calculations reveal the dissociation dynamics. This unimolecular decomposition reaction is proposed to proceed along two parallel reaction coordinates that originate with the rate-limiting Ni⁺ oxidative addition into either the OC-CH₃ or OC-C₂H₅ σ-bond in the butanone molecule. Rate constant values for the activation of both bonds are determined.	en_US
dc.description.degree	Ph.D.	en_US
dc.identifier.citation	Dee, S. J.; Castleberry, V. A.; Villarroel, O. J.; Laboren, I. E.; Frey, S. E.; Ashley,D.; Bellert, D. J. "Rate-Limiting Step in the Low-Energy Unimolecular Decomposition Reaction of the Ni+Acetone into Ni+CO + Ethane." Journal of Physical Chemistry A 113, (2009): 14074-14080.	en_US
dc.identifier.citation	Castleberry, V. A.; Dee, S. J.; Villarroel, O. J.; Laboren, I. E.; Frey, S. E.; Bellert, D. J. "The Low-Energy Unimolecular Reaction Rate Constants for the Gas Phase, Ni+-Mediated Dissociation of the C-C s-Bond in Acetone" Journal of Physical Chemistry A 113, (2009): 10417-10424.	en_US
dc.identifier.citation	Dee, S. J.; Castleberry, V. A.; Villarroel, O. J.; Laboren, I. E.; Bellert, D. J. "Low-Energy Reaction Rate Constants for the Ni+-Assisted Decomposition of Acetaldehyde: Observation of C-H and C-C Activation." Journal of Physical Chemistry A 114, (2010): 1783-1789.	en_US
dc.identifier.citation	Laboren, I. E.; Villarroel, O. J.; Dee, S. J.; Castleberry, V. A.; Klausmeyer, K.;Bellert, D. J. "Reaction Rate Constants and Mechanistic Detail of the Ni+ + Butanone Reaction." Journal of Physical Chemistry A 115, (2011): 1810-1820.	en_US
dc.identifier.uri	http://hdl.handle.net/2104/8268
dc.language.iso	en_US	en_US
dc.publisher		en
dc.rights	Baylor University theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission. Contact librarywebmaster@baylor.edu for inquiries about permission.	en_US
dc.rights.accessrights	Worldwide access	en_US
dc.subject	Unimolecular decomposition.	en_US
dc.subject	Reaction rate constant.	en_US
dc.title	Kinetics and mechanistic detail of Ni⁺ assisted organic decomposition reaction at low internal energies.	en_US
dc.type	Thesis	en_US