EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Interference of spin splittings in magneto-oscillation phenomena in two-dimensional systems

The spin splitting caused by the terms linear in wavevector in the effective Hamiltonian containing can give rise to the new magneto-oscillation phenomena in two-dimensional systems. It is shown that the joint action of the spin-dependent contributions due to the heterostructure asymmetry and to the lack of inversion center in the bulk material suppresses beats that arise in the magneto-oscillation phenomena in the presence of the terms of only one of these types.     

Field Theory Methods in Classical Dynamics

A Dirac picture perturbation theory is developed for the time evolution operator in classical dynamics in the spirit of the Schwinger–Feynman–Dyson perturbation expansion and detailed rules are derived for computations. Complexification formalisms are given for the time evolution operator suitable for phase space analyses, and then extended to a two-dimensional setting for a study of the geometrical Berry phase as an example. Finally a direct integration of Hamilton's equations is shown to lead naturally to a path integral expression, as a resolution of the identity, as applied to arbitrary functions of generalized coordinates and momenta.     

Three-dimensional radiative transfer in an anisotropically scattering, semi-infinite medium: generalized reflection function

Three-dimensional radiative transfer in an anisotropic scattering medium exposed to spatially varying, collimated radiation is studied. The generalized reflection function for a semi-infinite medium with a very general scattering phase function is the focus of this investigation. An integral transform is used to reduce the three-dimensional transport equation to a one-dimensional form, and a modified Ambarzumian's method is applied to formulate a nonlinear integral equation for the generalized reflection function. The integration is over both the polar and azimuthal angles; hence, the integral equation is said to be in the double-integral form. The double-integral, reflection function formulation can handle a variety of anisotropic phase functions and does not require an expansion of the phase function in a Legendre polynomial series. Complicated kernel transformations of previous single-integral studies are eliminated. Single and double scattering approximations are developed. Numerical results are presented for a Rayleigh phase function to illustrate the computational characteristics of the method and are compared to results obtained with the single-integral method. Agreement between the two approaches is excellent; however, as the transform variable increases beyond five the number of quadrature points required for the double-integral method to produce accurate solutions significantly increases. A new interpolation scheme produces accurate results when the transform variable is large.     

Computer simulation of selective absorption of radiation by the components of a light-scattering layer

A method of calculating the partial characteristics of radiation absorption by the components of light-scattering disperse layers is proposed. This method is based on statistical modeling (the Monte Carlo method). The absorptivities of photographic gelatin and silver bromide microcrystals and the corresponding distributions of the absorbed energy over the layer thickness are calculated using the example of an interaction between actinic radiation and silver halide photographic layers in the wavelength range λ=200–440 nm. The following structural parameters of the photographic layer are used in the calculation: the mean size of emulsion crystals d=0.5 μm; the polydispersity C _V =25%; the volume concentrations C _V =10, 20, and 30%; and the thickness of the emulsion layer H=10 μm.     

A comprehensive study of the long pulse Nd:YAG laser drilling of multi-layer carbon fibre composites

The results of an extensive experimental study of the free running Nd:YAG laser drilling of a multi-layer carbon fibre composite, where adjacent layers have differently orientated fibres, are reported. For holes drilled with the laser operating in fixed-Q mode at 1064 nm, parallel sections of blind holes illustrating discontinuities in the hole size along a given section direction will be shown to occur at the interface between adjacent layers. An explanation for this effect is proposed. Detailed single pulse drilling characteristics will be presented illustrating the exit hole diameter as a function of pulse energy and material thickness. These characteristics illustrate a ‘stable' drilling regime in which the exit hole diameters are least sensitive to changes in pulse energy or material thickness and a less ‘stable' regime in which they are more strongly dependent on these parameters. Drilling characteristics will be given for two different beam qualities, illustrating the greater drilling depth and reduced hole size achievable with an improved beam quality. Finally holes drilled through a 2 mm thick sample of material with multiple pulses are considered. Size distribution curves for entrance and exit holes will be presented. The total energy required (number of pulses × pulse energy) to drill through 2 mm thick material will be reported as a function of pulse energy in stationary air and argon atmospheres and in a partial vacuum, illustrating a threshold energy which is dependent upon the drilling atmosphere. The threshold energies will be discussed with reference to plasma formation and the reactivity of the drilling atmosphere.     

Mass transport in metals under intensive impulse reactions

An unusually high mobility of atoms under intensive impulse reactions is explained by the behavior of point defects at the shock wave front. It is shown that either a shock wave front or moving dislocations can capture the interstitials, or they can be thermally activated in the direction of the shock wave propagation.     

A method for computing the IR radiation of molecular gas jets in the volume approximation

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 3, pp. 478–484, September, 1991.     

Specific features of photoisomerization of provitamin D 3 in a nematic liquid crystal

Photoisomerization of provitamin D ₃ (7-dehydrocholesterol) in a nematic liquid crystal (ZLI-1695, Merck) is investigated in detail by UV absorption spectroscopy. It is found that dissolution of chiral molecules of provitamin D ₃ induces the cholesteric phase in a nematic. The spectral kinetics of photoisomerization in this phase changes significantly from that in an ethanol solution. A sharp nonmonotonic dependence of the increase in accumulation of trans isomer tachysterol in a liquid crystal matrix with a decrease in the induced cholesteric pitch from 2200 to 25 μm is revealed.