Titanium Superoxide as a Carrier of a "Long-Lived" Superoxide Anion: An Ab Initio Investigation.

Abstract

The photoinduced generation of a superoxide anion on the surface of a semiconductor photocatalyst is usually attributed to the reduction of O2 with conduction-band electrons. In the current work, the reaction of TiO2 with O2 giving rise to TiO4 in superoxide and peroxide states has been investigated with ab initio (CAS, CCSD) and DFT (B3LYP) calculations. The ground triplet state and two substates (open-shell singlet (OSS) and closed-shell singlet (CSS)) of a doubly degenerate excited singlet state (a1Δg) are considered as reactive states of oxygen, participating in spontaneous or photoinduced processes, respectively. The triplet and OSS singlet states of TiO4 contain O2- as structural units and can be defined as titanium superoxides. Both states have energy less than the level of the initial pair TiO2+O2 by about 30 kcal/mol. The CSS state of TiO4 has a diperoxide structure Ti4+(O22-)2 and also lies in energy below the initial pair TiO2+3O2. Titanium superoxide is considered to be the carrier of an "exceptionally stable" and "long-lived" superoxide anion, which was earlier synthesized or detected on the surface of TiO2. The low-energy location of the conical intersections on the way from reagents to 3TiO4 allows us to explain the literature data on the spontaneous generation of the "long-lived" superoxide anion on the TiO2 surface.