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Adsorption and dissociation of carbon trioxide on Ag(100)
Author(s) -
Soo TszYan,
Qin Changyong
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22035
Subject(s) - endothermic process , adsorption , chemistry , enthalpy , dissociation (chemistry) , ionic bonding , density functional theory , inorganic chemistry , crystallography , computational chemistry , thermodynamics , ion , organic chemistry , physics
Abstract Using density functional theory methods, we have studied carbon trioxide, its adsorption and dissociation on Ag(100). In the gas phase, two isomers are found, D 3 h and C 2 v , with the latter of 2.0 kcal mol −1 lower in energy at the PW91PW91/6−31G(d) level. For CO 3 on Ag(100), the calculated adsorption energy is 91.2 and 89.1 kcal mol −1 for the bi‐coord perpendicular and tri‐coord parallel structures, respectively. Upon the adsorption, 0.50 ∼ 0.56 electron is transferred from silver to CO 3 , indicative of significant ionic characters of the adsorbate‐surface bonding. In addition, the geometry of CO 3 is largely changed by its strong interaction with silver. For CO 3(ad) → O (ad) + CO 2(gas) , the energy barrier is calculated to be 19.8 kcal mol −1 through the bi‐coord path. The process is endothermic with an enthalpy change of +17.3 ∼ +26.7 kcal mol −1 and the weakly chemisorbed CO 2 is identified as an intermediate on the potential energy surface. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010