TY - JOUR
T1 - On the behavior of Brønsted-Evans-Polanyi relations for transition metal oxides
AU - Vojvodic, Aleksandra
AU - Vallejo, Federico Calle
AU - Guo, Wei
AU - Wang, Shengguang
AU - Toftelund, Anja
AU - Studt, Felix
AU - Martinez, Jose Ignacio
AU - Shen, Juan
AU - Man, Isabela Costinela
AU - Rossmeisl, Jan
AU - Bligaard, Thomas
AU - Nørskov, J. K.
AU - Abild-Pedersen, Frank
PY - 2011
Y1 - 2011
N2 - Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a "cyclic" behavior in the transition state characteristics upon change of the active transition metal of the oxide. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3602323]
AB - Versatile Brønsted-Evans-Polanyi (BEP) relations are found from density functional theory for a wide range of transition metal oxides including rutiles and perovskites. For oxides, the relation depends on the type of oxide, the active site, and the dissociating molecule. The slope of the BEP relation is strongly coupled to the adsorbate geometry in the transition state. If it is final state-like the dissociative chemisorption energy can be considered as a descriptor for the dissociation. If it is initial state-like, on the other hand, the dissociative chemisorption energy is not suitable as descriptor for the dissociation. Dissociation of molecules with strong intramolecular bonds belong to the former and molecules with weak intramolecular bonds to the latter group. We show, for the prototype system La-perovskites, that there is a "cyclic" behavior in the transition state characteristics upon change of the active transition metal of the oxide. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3602323]
U2 - 10.1063/1.3602323
DO - 10.1063/1.3602323
M3 - Journal article
C2 - 21721645
SN - 0021-9606
VL - 134
SP - 244509
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 24
ER -