Redox troponization as a novel method for the synthesis of stereoisomeric Eschenmoser's oximes and related non-benzenoid aromatic systems

A novel method for the synthesis of the oxime of 4-methyl-2,4,6-cycloheptatrien-1-one (Eschenmoser's oxime) is proposed. The method involves redox enlargement of the ring of 4-dibromomethyl-4-methyl-2,5-cyclohexadien-1-one oxime through the action of Ni(PPh₃)₄ in DMF (in the presence of Zn). The product is formed as a mixture ofsyn- andanti-forms readily interconverting in solutions. A similar reaction of 4-methyl-4-trichloromethyl-2,5-cyclohexadien-1-one oxime afforded the dimer of agem--centered semiquinoid carbene (1,2-bis-(1-methyl-4-oxyimino-2,5-cyclohexadienyl)-1,2-dichloroethylene), together withsyn- andanti-isomers of 4-chloro-5-methyl-2,4,6-cycloheptatrien-1-one oxime, which are readily separable but also quickly interconverting in solutions. For the latter compounds, the complete¹H NMR assignment of the stereoisomeric structures has been carried out.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 519–523, March, 1995.The authors are grateful to the International Science Foundation (Grant MHW000) as well as the Russian Foundation for Basic Research (Project No. 94-03-08873) for the financial support of the work.     

Terahertz laser based on optically pumped graphene: Model and feasibility of realization

We consider a terahertz laser based on optically pumped graphene layer and bilayer as the active media and suggested waveguide structure. Using the developed model, we calculate the spectral dependences the dynamic conductivity of the optically pumped graphene layer and bilayer associated with the interband and intraband transitions, estimate the pumping optical power required for lasing, and demonstrate the feasibility of realization of such a laser. The article is published in the original.     

Optical band gap width in GaAs in megagauss magnetic fields

The band gap width in GaAs in magnetic fields of up to 10 MG is calculated using a five-band kp model. The selection rules for interband electron transitions in strong magnetic fields are found, and the dependences of the interband transition probabilities on a magnetic field are calculated. The electronic spectra calculated in the five-band model are compared with those calculated in the Kane model and in the tight-coupling approximation. The calculations are shown to agree with experimental data if the contribution from the density-of-states tails and excitonic effects to light absorption is taken into account.     

Anomalous characteristics of lasers with a large number of quantum wells

Semiconductor lasers with an active region containing six quantum wells are investigated experimentally. The temperature dependences of working characteristics (threshold current density, external differential quantum efficiency, and directional pattern) are analyzed. Anomalous behavior of the temperature dependence of the threshold current and external differential quantum efficiency, associated with a negative characteristic temperature and a decrease in the quantum efficiency of radiation upon a decrease in temperature, is detected. A narrowing of the directional patterns in the plane perpendicular to the p-n junction upon an increase in temperature is revealed.     

The formation of the superheavy hydrogen isotope <Superscript>6</Superscript>H in the absorption of stopped π<Superscript>−</Superscript>-mesons by nuclei

An experimental search for the superheavy hydrogen isotope ⁶H was conducted through studying the absorption of stopped π^?-mesons by ⁹Be and ¹¹B nuclei. A structure in the missing mass spectrum caused by the resonance states of ⁶H was observed in three reaction channels, namely, ⁹Be(π^?, pd)X, ¹¹B(π^?, d³He)X, and ¹¹B(π^?, p⁴He)X. The parameters of the lowest state E_r=6.6±0.7 MeV and Γ=5.5±2.0 MeV (E_r is the resonance energy with respect to the disintegration into the triton and three neutrons) are evidence that ⁶H is a more weakly bound system than ⁴H and ⁵H. Three excited states of ⁶H were observed. Their resonance levels (E_1r=10.7±0.7 MeV, Γ_1r=4±2 MeV, E_2r=15.3±0.7 MeV, Γ _2r=3±2 MeV, and E_3r=21.3±0.4 MeV, Γ_3r=3.5±1.0 MeV) are energetically capable of disintegrating into six free nucleons.     

GaAsSb/GaAs quantum well growth by MOCVD hydride epitaxy with laser sputtering of antimony

A new method of obtaining quantum-size GaAs_1−x Sb_x (x⩽0.45) layers is proposed. The method consists in laser vaporization of solid metallic antimony near the substrate directly in the reactor. The antimony concentration is set by the antimony sputtering time with the arsine flux shut off. The polarization of the photoluminescence of the obtained layers indicates the formation of quantum wires. The heterostructures obtained are used to fabricate laser diodes. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 1, 84–88 (10 July 1998)     

Fano resonance in the impurity photoconductivity spectrum of InP doped with shallow donors

The Fano resonances in the impurity photoconductivity spectra of n-InP are investigated theoretically and experimentally. It is shown that the calculations describe the experimental data with an accuracy of up to 20%.     

Near-field effect in the absorption spectrum of impurities in crystals

The effect of the near-field interaction of shallow donors in GaAs on the intracenter absorption spectrum of impurities has been considered. It has been shown that the near-field interaction leads to broadening of the absorption line, which increases with the donor density. The absorption line shape is no longer Lorentzian: its low-frequency wing becomes more prolonged than the high-frequency wing.     

Dynamics of the cascade capture of electrons by charged donors in GaAs and InP

The times for the cascade capture of an electron by a charged impurity have been calculated for pulsed and stationary excitations of impurity photoconductivity in GaAs and InP. The characteristic capture times under pulsed and continuous excitations are shown to differ noticeably both from each other and from the value given by the Abakumov–Perel–Yassievich formula for a charged impurity concentration greater than 10¹⁰ cm^–3. The cause of this difference has been established. The Abakumov–Perel–Yassievich formula for the cascade capture cross section in the case of stationary excitation has been generalized. The dependences of the cascade capture rate on the charged impurity concentration in GaAs and InP have been found for three temperatures in the case of pulsed excitation.