Computations on C 84O

Thermodynamic, kinetic and photochemical stability

Zdeněk Slanina, Filip Uhlík, Libor Juha, Kazutoshi Tanabe, Ludwik Adamowicz, Eiji Osawa

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Fullerene oxides were the first observed fullerene derivatives and they have naturally attracted attention of both experiment and theory. C 60O has represented a long standing case of experiment-theory disagreement, and there has been a similar problem with C 60O 2 - both cases were explained by kinetic rather than thermodynamic control. In this contribution, we report the first computations of C 84O. The computations are carried out with the PM3 quantum-chemical semiempirical method. Thermodynamic stabilities are evaluated for the electronic singlet and triplet states. The triplet states are computed at both restricted open-shell Hartree-Fock (ROHF) and unrestricted open-shell Hartree-Fock levels. The computations focus on the two most abundant C 84 isomers - D 2 and D 2d, and especially deal with additions to their shortest and longest bonds. The D 2/long structure is the lowest-energy species. The PM3/ROHF energy ordering of the C 84O isomers in the first triplet electronic state is exactly the same as in the singlet electronic state and the relative energies are also quite similar. On the other hand, the kinetic stability order is just reversed compared to the thermodynamic order. Hence, for relatively short reaction times the C 84O D 2/short isomer should primarily be formed (in spite of the fact that it should be, thermodynamically, the least stable in the studied set). The computations point out various stability selection rules controlling production of fullerene-based materials.

Original languageEnglish (US)
Pages (from-to)129-133
Number of pages5
JournalJournal of Molecular Structure: THEOCHEM
Volume684
Issue number1-3
DOIs
StatePublished - Sep 27 2004

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Fullerenes
Thermodynamics
Isomers
fullerenes
thermodynamics
Kinetics
isomers
kinetics
Electronic states
atomic energy levels
electronics
Oxides
reaction time
energy
Thermodynamic stability
Experiments
Derivatives
oxides

Keywords

  • C
  • Fullerene oxides
  • Fullerenes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

Computations on C 84O : Thermodynamic, kinetic and photochemical stability. / Slanina, Zdeněk; Uhlík, Filip; Juha, Libor; Tanabe, Kazutoshi; Adamowicz, Ludwik; Osawa, Eiji.

In: Journal of Molecular Structure: THEOCHEM, Vol. 684, No. 1-3, 27.09.2004, p. 129-133.

Research output: Contribution to journalArticle

Slanina, Zdeněk ; Uhlík, Filip ; Juha, Libor ; Tanabe, Kazutoshi ; Adamowicz, Ludwik ; Osawa, Eiji. / Computations on C 84O : Thermodynamic, kinetic and photochemical stability. In: Journal of Molecular Structure: THEOCHEM. 2004 ; Vol. 684, No. 1-3. pp. 129-133.
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