title: Comparative study of O2 dissociation on various metalloporphyrins.
abstract: We investigate O(2) interaction with various metalloporphyrins (MnP, FeP, CoP, and NiP) using ab initio calculations based on density-functional theory. We discuss the trends in the activation barriers for the O-O bond cleavage in relation to the geometric, vibrational, electronic, and energetic properties of the systems. Whether the lowest unoccupied molecular orbital-highest occupied molecular orbital (LUMO-HOMO) levels of the metalloporphyrins involve the corresponding metal centers depends on the d orbital occupancies of the metals. We found that activation barriers for the O(2) dissociation can be mainly determined from the LUMO-HOMO characters of the metalloporphyrins, and consequently the FeP is the best catalyst with respect to the O(2) interaction from adsorption to dissociation.
authors.affiliation: Department of Applied Physics, Osaka University, Suita, Japan.
authors.forename: Muneyuki
authors.initials: M
authors.lastname: Tsuda
authors.forename: Eben Sy
authors.initials: ES
authors.lastname: Dy
authors.forename: Hideaki
authors.initials: H
authors.lastname: Kasai