Quantum chemical prediction of reaction pathways and rate constants for the reactions of O x (x = 1 and 2) with pristine and defective graphite (0001) surfaces

S. C. Xu, Hui Lung Chen, Ming-Chang Lin*

*Corresponding author for this work

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

We present reaction pathways for adsorption reactions of the O atom and O 2 molecule in the pristine and monovacancy defective graphite (0001) based on quantum chemical potential energy surfaces (PESs) obtained by the dispersion-augmented density-functional tight-binding (DFTB-D) method. We use a dicircumcoronene C 96H 24 (L0D) graphene slab as the pristine graphite (0001) model and dicircumcoronene C 95H 24 (LIV) as the graphite (0001) monovacancy defect model. We found that the adsorption reactions of O and O 2 on the L0D surface can produce defects on the graphite surface. O can yield CO, while O 2 can yield both CO and CO 2 molecules. The adsorption reactions of the O and O 2 on the LIV surface can produce a 2-C defective graphite surface and CO, and CO and CO 2, respectively. The O and O 2 more readily oxidize the defected surface, LIV, than the defect-free surface, L0D. On the basis of the computed reaction pathways, we predict reaction rate constants in the temperature range between 300 and 3000 K using Rice-Ramsperger-Kassel- Marcus (RRKM) theory. High-temperature quantum chemical molecular dynamics simulations at 3000 K based on on-the-fly DFTB-D energies and gradients support the results of our PES studies.

Original languageEnglish
Pages (from-to)1841-1849
Number of pages9
JournalJournal of Physical Chemistry C
Volume116
Issue number2
DOIs
StatePublished - 19 Jan 2012

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