Photochemistry of dibenzo-1,4-dioxins: intramolecular rearrangement-reduction through observable 2,2′-biphenylquinones

The photochemistry of dibenzo-1,4-dioxin (7) and 2,3,7,8-tetramethyldibenzo-1,4-dioxin (15) — both of which have the parent ring system of the well-known enrimental contaminant dioxin— has been studied in aqueous solution and in selected organic solvents. It is shown that a novel intramolecular photorearrangement is the major mode of reaction for 7 and the exclusive reaction for 15, giving rise to observable (by UV—Vis spectrophotometry) intermediate 2,2′-biphenylquinones. Subsequent reduction by the organic co-solvent gives rise to 2,2′-biphenols as major or exclusive product. Thus, photolysis of these compounds generates oxidizing agents in the biphenylquinones. Photolysis in the presence of added N_aBH₄ resulted is greatly enhanced yields of biphenols along with more than 90% material balance. These findings have relevance to dioxin photodecomposition, which can be used as a method for its destruction.     

Synthesis and photophysical properties of fluorescent 2-aryl-1,3-dialkylbenzimidazolium ions and a l-alkyl-2-arylbenzimidazole with excited state intramolecular proton-transfer

To improve the solubility, photostability and fluorescence quantum yield (Φ) of 2-arylbenzimidazolium ions the N-1 hydrogen was replaced by an alkyl group before N-3 was quatemized; this substitution did not reduce Φ, proving the absence of steric inhibition to attainment of coplanarity in the excited state. A related symmetrical 2,2′-arylenebis(1,3-dimethyldibenzimidazolium ion) had Φ = 0.86. The related 2,5-bis(1-methyl-2-benzimidazolyl)phenol had Φ = 0.38 at 22° as well as a very large Stokes' shift due to proton-transfer. These findings supported a new insight into the electron distribution of the first excited singlet state of oligophenylenes. The compounds are of interest as laser dyes and scintillation fluors.     

A semiclassical reactive flux method for the calculation of condensed phase activated rate constants

A semi classical reactive flux algorithm for calculating thermally activated rate constants is presented which is based on a semi-classical transition state theory due to Chapman, Garrett and Miller [J. Chem. Phys. 63 (1975) 2710]. This reactive flux technique, when combined with the semiclassical TST, enables one to describe dynamical recrossings of the transition state on the same footing as tunneling effects. Most importantly, the method is readily applied to nonlinear multidimensional systems over a wide range of temperatures. It will be shown that the method works very well for a variety of existing models.     

Laboratory simulation of atmospheric turbulence-induced optical wavefront distortion

Real-time liquid crystal television-based technique for simulating optical wavefront distortion due to atmospheric turbulence is presented and demonstrated. A liquid crystal television (LCTV) operating in the “phase mostly” mode was used as an array of spatially correlated phase delays. A movie of the arrays in motion was then generated and displayed on the LCTV. The turbulence simulation system was verified by passing a collimated and doubled diode pumped Nd:YVO₄ laser beam (532 nm) through the transparent LCTV screen. The beam was then passed through a lens and the power spectra of the turbulence information carrying beam was detected as a measure of the far-field distribution. The same collimated laser beam, without the LCTV, was also transmitted down an open-air range and the power spectra detected as a measure of a real far-field distribution. Accepted turbulence parameters were measured for both arrangements and then compared.