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Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
12:08

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Fulvenallene decomposition kinetics.

Daniela Polino1, Carlo Cavallotti

  • 1Department Chimica, Materiali e Ingegneria Chimica G. Natta, Politecnico di Milano, via Mancinelli 7, 20131 Milano, Italy.

The Journal of Physical Chemistry. A
|August 9, 2011
PubMed
Summary
This summary is machine-generated.

High-temperature reactions of fulvenallene were studied. Two decomposition pathways were identified, with intersystem crossing being rate-limiting for one, impacting reaction rates significantly.

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Area of Science:

  • Chemical kinetics
  • Theoretical chemistry
  • Combustion chemistry

Background:

  • Benzyl radical decomposition yields fulvenallene, a less-studied reactive intermediate.
  • Understanding fulvenallene's high-temperature reactivity is crucial for combustion and chemical process modeling.

Purpose of the Study:

  • Investigate the high-temperature decomposition kinetics of fulvenallene.
  • Determine the dominant reaction pathways and their rate constants.
  • Assess the influence of intersystem crossing on decomposition channels.

Main Methods:

  • Utilized a 1D Master Equation (ME) model integrated with a stochastic kinetic Monte Carlo code.
  • Calculated rate constants using RRKM theory on a detailed Potential Energy Surface (PES).
  • Incorporated Landau-Zener theory for microcanonical intersystem crossing frequency calculations.

Main Results:

  • Identified two primary decomposition channels: fulvenallenyl radical + H (singlet PES) and acetylene + cyclopentadienylidene (triplet PES via intersystem crossing).
  • Found that the cyclopentadienylidene channel is only slightly faster than the fulvenallenyl radical channel.
  • Demonstrated that intersystem crossing is rate-limiting for the singlet-to-triplet pathway, increasing rates by 2-3 fold when removed.

Conclusions:

  • Both identified decomposition channels are likely active between 1500-2000 K and 0.05-50 bar.
  • Intersystem crossing significantly influences the overall decomposition rate, highlighting its importance.
  • Provides channel-specific rate constants as a function of temperature and pressure for kinetic modeling.