화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.118, No.13, 3553-3558, 2014
Ab Initio Modeling of the Effect of Oxidation Coupled with HnO Deprotonation on Carboxylate Ligands in Mn/Ca Clusters
Oxidation of some manganese complexes containing both carboxylate and water/hydroxo ligands does not result in changes to the carboxylate stretching frequencies. The water oxidizing complex of photosystem H is one motivating example. On the basis of electronic structure theory calculations, we here suggest that the deprotonation of water or hydroxo ligands minimizes changes in the vibrational frequencies of coligating carboxylates, rendering the carboxylate modes "invisible" in FTIR difference spectroscopy. This deprotonation of water/hydroxo ligands was also found to balance the redox potentials of the Mn(II)/Mn(III) and Mn(III)/Mn(IV) couples, allowing the possibility for successive manganese oxidations at a relatively constant redox potential.