Excited-State Chemistry: Photocatalytic Methanol Oxidation by Uranyl@Zeolite through Oxygen-Centered Radicals.

We have elucidated the complex reaction network of partial methanol oxidation, H3COH + O2 → H2CO + H2O2, at a visible-light-activated actinide photocatalyst. The reaction inertness of C-H bonds and O═O diradicals at ambient conditions is overcome through catalysis by photoexcited uranyl units (*UO22+) anchored on a mesoporous silicate. The electronic ground- and excited-state energy hypersurfaces are investigated with quasirelativistic density-functional and ab initio correlated wave function approaches. Our study suggests that the molecular cluster can react on the excited energy surface due to the longevity of excited uranyl, typical for f-element compounds. The theoretically predicted energy profiles, chemical intermediates, related radicals, and product species are consistent with various experimental findings. The uranyl excitation opens various reaction pathways for the oxidation of volatile organic compounds (VOCs) by "hole-driven hydrogen transfer" (HDHT) through several exothermic steps over low activation barriers toward environmentally clean or chemically interesting products. Quantum-chemical modeling reveals the high efficiency of the uranyl photocatalysis and directs the way to further understanding and improvement of VOC degradation, chemical synthesis, and biologic photochemical interactions between uranyl and the environment.

A simple density functional fractional occupation number procedure to determine the low energy transition region of spin-flip reactions.

A computationally simple three-step procedure to survey the energy landscape and to determine the molecular transition structure and activation energy at the intersection of two weakly coupled electronic potential energy surfaces of different symmetry is suggested. Only commercial software is needed to obtain the transition states of, for instance, spin-flip reactions. The computational expense is only two to three times larger than that of the standard determination of an adiabatic reaction path. First, the structures of the two electronic initial and final states along a chosen reaction coordinate are individually optimized. At the "projected crossing," the two states have the same energy at the same value of the reaction coordinate, but different state-optimized partial structures. Second, the unique optimized structure of a low energy crossing point between the two states is determined with the help of the density functional fractional occupation number approach. Finally, the respective energy of the two states at the crossing is estimated by a single point calculation. The prescription is successfully applied to some simple topical examples from organic and from inorganic chemistry, respectively, concerning the spin-flip reactions (3)H(3)CS(+)-->(1)H(2)CSH(+) and (7)MoCO(2)-->(5)MoCO(2)-->(3)OMoCO.