The detection methods and generation mechanisms of the intrinsic reactive oxygen species (ROS), i.e., superoxide anion radical (•O2–), hydrogen peroxide (H2O2), singlet oxygen (1O2), and hydroxyl radical (•OH) in photocatalysis, were surveyed comprehensively. Consequently, the major photocatalyst used in heterogeneous photocatalytic systems was found to be TiO2. However, besides TiO2 some representative photocatalysts were also involved in the discussion. Among the various issues we focused on the detection methods and generation reactions of ROS in the aqueous suspensions of photocatalysts. On the careful account of the experimental results presented so far, we proposed the following apprehension: adsorbed •OH could be regarded as trapped holes, which are involved in a rapid adsorption–desorption equilibrium at the TiO2–solution interface. Because the equilibrium shifts to the adsorption side, trapped holes must be actually the dominant oxidation species whereas •OH in solution would exert the reactivity...

Generation and Detection of Reactive Oxygen Species in Photocatalysis

Lambda-type doubling parameters for molecules in Π electronic states of triplet and higher multiplicity

Analysis of perturbations in the A2Π-X2Σ+ “Red” system of CN

The theory of Van der Waals complexes formed from atoms and open‐shell (Σ and Π) diatomic molecules is developed, paying particular attention to the quantum numbers that are conserved in the complex and the angular momentum coupling cases that may be observed. Complexes formed from diatoms in multiplet Σ states may exhibit several different coupling schemes closely analogous to Hund’s coupling cases for diatomic molecules. Complexes formed from diatoms in Π states usually exhibit a coupling scheme in which the (signed) projection P of the diatom angular momentum j onto the intermolecular axis is nearly conserved. Correlation diagrams showing the bending energy levels as a function of potential anisotropy are given for complexes containing diatomic molecules in both Σ and Π states. The transition from free internal rotor quantum numbers to near‐rigid bender quantum numbers with increasing anisotropy is investigated. The cases of Ar–OH and Ne–OH are considered as examples.

The dynamics of open-shell Van der Waals complexes

A summary is given of the laboratory measurements of the rotational spectra of eight new carbon chains: the cyanopolyynes HC11N and HC13N; the carbon chain radicals C7H, C8H, C9H, and C11H; and the cumulene carbenes H2C5 and H2C6. Measured line frequencies and derived spectroscopic constants are listed for all eight, and rest frequencies for the astronomically important transitions that are not easily calculated are tabulated. With our laboratory measurements, four of the new carbon chains have already been detected in at least one astronomical source; the remaining four should be detectable with existing large centimeter- or millimeter-wave telescopes.

Eight New Carbon Chain Molecules

Measurements of the gas-phase E.P.R. spectra of OH in the J = 9/2 and 11/2 levels of the X2II state at 26 GHz and 35 GHz respectively are reported. Confocal and semi-confocal optical resonators have been used in place of the more conventional microwave cavities for these experiments. The data are analysed, together with previous measurements by Radford on other rotational levels in the determination of six independent g factors: These parameters are interpreted in terms of the electronic structure of the OH radical. In agreement with previous workers, it is found that the major contaminant of the X2II state is the A2Σ+ state and that this pair of states is a good example of Van Vleck's pure precession hypothesis.

J.M. Brown

Papers

A determination of fundamental Zeeman parameters for the OH radical