Quantum chemical prediction of reaction pathways and rate constants for reactions of NO and NO2 with monovacancy defects on graphite (0001) surfaces

S. C. Xu, S. Irle*, Ming-Chang Lin

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations


We present reaction pathways for adsorption reactions of NO and NO 2 molecules in the vicinity of monovacancy defects on graphite (0001) based on quantum chemical potential energy surfaces (PESs) obtained by B3LYP and dispersion-augmented density-functional tight-binding (DFTB-D) methods. To model the graphite (0001) monovacancy defects, finite-size molecular model systems up to the size of dicircumcoronene (C95H24) were employed. We find that the reactions of NOx on the monodefective graphite surface are initiated by rapid association processes with negligible barriers, leading to nitridation and oxidation of the graphite surface, and eventually producing gaseous COx, NO, and CN species leaving from an even more defective graphite surface. 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 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)8375-8382
Number of pages8
JournalJournal of Physical Chemistry C
Issue number18
StatePublished - 13 May 2010

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