SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA.
J Chem Phys. 2011 Jun 28;134(24):244509. doi: 10.1063/1.3602323.
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.
从密度泛函理论中发现了广泛的过渡金属氧化物（包括金红石和钙钛矿）的多功能布朗斯特-埃文斯-波尔兹曼（BEP）关系。对于氧化物，该关系取决于氧化物的类型、活性位和离解分子。BEP 关系的斜率与过渡态中吸附物的几何形状强烈耦合。如果它类似于终态，那么离解化学吸附能可以被视为离解的描述符。另一方面，如果它类似于初始状态，则离解化学吸附能不适合作为离解的描述符。具有强分子内键的分子属于前一种，而具有弱分子内键的分子属于后一种。我们以原型体系 La 钙钛矿为例，表明在氧化物的活性过渡金属发生变化时，过渡态特性存在“循环”行为。
