Ab initio calculations of vibronic activity in phosphorescence microwave double resonance spectra of p-dichlorobenzene

The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet–triplet (³B_1u¹A_g) transition through a number of vibronic subbands. The second order spin–orbit coupling (SOC) contribution to the spin splitting of the ³B_1u (^3*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin–spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet–singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.Acknowledgment O. R.-P. would like to thank the European MOLPROP network for support. The authors thank Alexander Baev for fruitful discussions. This work was supported by the Swedish Royal Academy of Science (KVA).     

Role of exchange interaction in spin catalysis mechanisms

Possible mechanisms are examined for spin catalysis, in which a reaction is accelerated through the action of a catalyst on the spin parameters of the system. Since the orbital and spin characteristics of electrons are interrelated through permutational symmetry (Pauli principle) by means of exchange interactions, this article examines the role of exchange in catalysis. Spin uncoupling has been found to play a role, not only for paramagnetic catalysts, but also for all types of catalysis.Cherkassy Engineering Technology Institute, 460 Shevchenko Boulevard, Cherkassy 257006, Ukraine. Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 32, No. 1, pp. 1–12, January–February, 1996. Original article submitted April 5, 1995.     

Calculation of the magnetophotoselective effect in reactions of triplet molecules

An expression for the initial chemically induced dynamic electron polarization produced according to a triplet mechanism under the conditions of pumping by polarized light has been obtained under the assumption that the fluctuations of the orientation of a molecule in a liquid have the character of an uncorrelated Markov process. The expression obtained is valid for arbitrary values of the magnetic field strength and the viscosity of the solvent. Numerical calculations of the chemically induced dynamic electron polarization have been carried out for slow molecular rotations and in weak magnetic fields.Translated from Teoreticheskaya i éksperimental'naya Khimiya, Vol. 24, No. 1, pp. 96–100, January–February, 1988.We thank V. E. Gluzberg for his assistance in carrying out the numerical calculations.     

Spin–orbit coupling in oxygen containing diradicals

Intermediate diradicals which occur in the Paterno–Büchi photocycloaddition and in the Norrish type I photoreactions have been calculated taking into account the spin–orbit coupling (SOC) between the singlet (S) and triplet (T) states. Reaction paths for the photocycloaddition of formaldehyde to ethene and the diradical products of the α-cleavage of cyclohexanone have been optimized by the MNDO CI method for a number of different singlet and triplet states. SOC integrals are calculated by an effective one-electron approximation. Intermediate diradicals in the Paterno–Büchi reaction and the SOC effects are also studied ab initio with CAS SCF geometry optimization in a TZV basis set. Both methods predict a large SOC matrix element between the S and T states in the course of the C–C attack, while the SOC integral is two orders of magnitude smaller for the diradical produced in the C–O attack. In the Norrish type I photoreaction the oxygen atom also produces some nonzero contribution to the SOC integral which governs intersystem crossing in a ·C–C· diradical. For the diradicals produced by the α-cleavage of cyclohexanone a vibronic interaction is responsible for the SOC mixing between the lowest S and T states. The importance of one-center versus two-center SOC contributions in diradicals is briefly discussed.     

Formation of porous matrices from lactide and ε-caprolactone copolymers in supercritical carbon dioxide medium

A series of lactide and ε-caprolactone copolymers containing 4–24 mol % of ε-caprolactone with 20- to 30-kDa molecular weights are synthesized. Based on them, porous materials are produced by foaming in supercritical carbon dioxide. The pore size was shown to decrease with increasing ε-caprolactone content in copolymer, while the porosity of the entire sample was not altered. The resulting pore size also decreases if 7 wt % polyethylene glycol is added to the initial monomer mixture. The Young’s modulus of the porous samples decreases with increasing ε-caprolactone content and when polyethylene glycol is added.     

Energy approach to considering multicomponent powder systems

The problems of formation of the structure of a dispersed multicomponent powder mixture in mixing are considered from an energy standpoint. The homogeneous state of a powder mixture is shown to be energetically more favorable than the state of its separation, since it has a lower free energy margin and a higher configurational entropy. Depending on external conditions, a mixture of homogeneous regions with different component concentrations can have a more stable state.     

Formation of a quasi-hollow beam of high-energy heavy ions using a multicell resonance RF deflector

The generation of matter in an extreme state with precisely measurable parameters is of great interest for contemporary physics. One way of obtaining such a state is to irradiate the end of a hollow cylindrical shell at the center of which a test material is kept at a temperature of several Kelvin by an annular beam of high-energy heavy ions. Under the action of the beam, the shell starts explosively expanding both outwards and inwards, compressing the material to an extremely high pressure without subjecting it to direct heating. A method of producing a hollow cylindrical beam of high-energy heavy ions using a resonance rf deflector is described. The deflection of the beam in two transverse directions by means of an rf electric field allows it to rotate about the longitudinal axis and irradiate an annular domain on the end face of the target.     

Supercontinuum generation under filamentation driven by intense femtosecond pulses in supercritical xenon and carbon dioxide

It is found that supercritical fluids are a unique source of multioctave supercontinuum radiation, which is generated upon filamentation of an intense femtosecond laser pulse. If the laser pulse power significantly exceeds the critical power of self-focusing, then a supercontinuum with a width of three and a half spectral octaves (from 350 to 2000 nm) is generated in supercritical xenon. The red wing of supercontinuum generated in supercritical carbon dioxide has the form of a plateau in the range from 1400 to 1900 nm, while the blue wing of the spectrum is almost completely attenuated.     

Synthesis of Supported Heterogeneous Catalysts by Laser Ablation of Metallic Palladium in Supercritical Carbon Dioxide Medium

To obtain a supported heterogeneous catalyst, laser ablation of metallic palladium in supercritical carbon dioxide was performed in the presence of a carrier, microparticles of γ-alumina. The influence of the ablation process conditions—including supercritical fluid density, ablation, mixing time of the mixture, and laser wavelength—on the completeness and efficiency of the deposition of palladium particles on the surface of the carrier was studied. The obtained composites were investigated by scanning and transmission electron microscopy using energy dispersive spectroscopy. We found that palladium particles were nanosized and had a narrow size distribution (2–8 nm). The synthesized composites revealed high activity as catalysts in the liquid-phase hydrogenation of diphenylacetylene.