Criegee intermediate inside fullerene cage: Evidence for size-dependent reactivity

Manoj Kumar, Jie Zhong, Xiao Cheng Zeng, Joseph S. Francisco

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In the theoretical calculations reported here, we show that the hydration of the Criegee intermediate within the sub-nanospace of fullerene cages occurs differently in different fullerenes, thereby providing evidence for the size-dependent reactivity inside these exotic carbon cages. Upon C 70 or C 84 encapsulation, the Criegee hydration occurs instantaneously without any activation barrier, whereas inside the C 120 cage, the hydration involves a small barrier of 4.4 kcal/mol. Our Born-Oppenheimer molecular dynamics simulations suggest that the Criegee intermediate and the product of its hydration, α-hydroxy methyl hydroperoxide, remain dynamically stable over 20 ps time scale at the 300 K, implying that fullerene cages provide a robust framework for reactivity.

Original languageEnglish (US)
Article number244301
JournalJournal of Chemical Physics
Volume148
Issue number24
DOIs
StatePublished - Jun 28 2018

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Fullerenes
Hydration
fullerenes
hydration
reactivity
Encapsulation
Hydrogen Peroxide
Molecular dynamics
Carbon
Chemical activation
activation
molecular dynamics
carbon
Computer simulation
products
simulation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Criegee intermediate inside fullerene cage : Evidence for size-dependent reactivity. / Kumar, Manoj; Zhong, Jie; Zeng, Xiao Cheng; Francisco, Joseph S.

In: Journal of Chemical Physics, Vol. 148, No. 24, 244301, 28.06.2018.

Research output: Contribution to journalArticle

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