標題: Quantum Chemical Prediction of Pathways; and Rate Constants for Reactions of CO and CO(2) with Vacancy Defects on Graphite (0001) Surfaces
作者: Xu, S. C.
Irle, S.
Musaev, D. G.
Lin, M. C.
應用化學系分子科學碩博班
Institute of Molecular science
公開日期: 29-Oct-2009
摘要: We present reaction pathways for adsorption of CO and CO(2) molecules in the vicinity of monovacancy defects on graphite (0001) based on B3LYP and dispersion-augmented density-functional tight-binding (DFTB-D) studies of the potential energy surfaces (PES) of these reactions. To model the graphite (0001) monovacancy defects, finite-size molecular model systems up to the size of dicircumcoronene (C(95)H(24)) were employed. We find that the CO molecule reacts readily with the monovacancy defects and partially "heals" the carbon hexagon network leading to the formation of a stable epoxide, whereas CO(2) oxidizes the defect via a dissociative adsorption pathway following CO elimination. We predict reaction rate constants in the temperature range between 300 and 3000 K using Rice-Ramsperger-Kassel-Marcus theory. 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.
URI: http://dx.doi.org/10.1021/jp9056994
http://hdl.handle.net/11536/6551
ISSN: 1932-7447
DOI: 10.1021/jp9056994
期刊: JOURNAL OF PHYSICAL CHEMISTRY C
Volume: 113
Issue: 43
起始頁: 18772
結束頁: 18777
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