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image/svg+xml Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Closed Access logo, derived from PLoS Open Access logo. This version with transparent background. http://commons.wikimedia.org/wiki/File:Closed_Access_logo_transparent.svg Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao RE.PUBLIC@POLIMI Res...arrow_drop_down
image/svg+xml Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Closed Access logo, derived from PLoS Open Access logo. This version with transparent background. http://commons.wikimedia.org/wiki/File:Closed_Access_logo_transparent.svg Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao
The Journal of Physical Chemistry A
Article . 2011 . Peer-reviewed
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Fulvenallene Decomposition Kinetics

Authors: POLINO, DANIELA; CAVALLOTTI, CARLO ALESSANDRO;

Fulvenallene Decomposition Kinetics

Abstract

While the decomposition kinetics of the benzyl radical has been studied in depth both from the experimental and the theoretical standpoint, much less is known about the reactivity of what is likely to be its main decomposition product, fulvenallene. In this work the high temperature reactivity of fulvenallene was investigated on a Potential Energy Surface (PES) consisting of 10 wells interconnected through 11 transition states using a 1 D Master Equation (ME). Rate constants were calculated using RRKM theory and the ME was integrated using a stochastic kinetic Monte Carlo code. It was found that two main decomposition channels are possible, the first is active on the singlet PES and leads to the formation of the fulvenallenyl radical and atomic hydrogen. The second requires intersystem crossing to the triplet PES and leads to acetylene and cyclopentadienylidene. ME simulations were performed calculating the microcanonical intersystem crossing frequency using Landau-Zener theory convoluting the crossing probability with RRKM rates evaluated at the conical intersection. It was found that the reaction channel leading to the cyclopentadienylidene diradical is only slightly faster than that leading to the fulvenallenyl radical, so that it can be concluded that both reactions are likely to be active in the investigated temperature (1500-2000 K) and pressure (0.05-50 bar) ranges. However, the simulations show that intersystem crossing is rate limiting for the first reaction channel, as the removal of this barrier leads to an increase of the rate constant by a factor of 2-3. Channel specific rate constants are reported as a function of temperature and pressure.

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
47
Top 10%
Top 10%
Top 10%
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