Asymptotic profile of solutions to nonlinear dissipative evolution system with ellipticity

We consider the Cauchy problem for the nonlinear dissipative evolution system with ellipticity on one dimensional space

New mechanism of the formation of the nanorelief on a surface irradiated by a femtosecond laser pulse

The kinetics of fast processes induced by an ultrashort laser pulse is considered. The reliefs remaining after the action of a series of ultrashort laser pulses {S. A. Akhmanov, V. I. Emelyanov, N. I. Koroteev, et al., Usp. Fiz. Nauk 147, 675 (1985) [Sov. Phys. Usp. 28, 1084 (1985)]; F. Costache, S. Kouteva-Arguirova, and J. Reif, Appl. Phys. A 79, 1429 (2004)} have been studied. A new mechanism of perturbing the surface of the initially ideal crystal face is described. First, the formation of a relief is induced by a single pulse. Second, the relief scale along the target surface is about the heating depth d _T ～ 10–100 nm rather than the pump-pulse wavelength λ_pump ～ 1 μm. Third, the formation of the relief is not attributed to the modulation of the electromagnetic field near the surface due to the interference of the incident light wave with the electromagnetic surface waves on the initial perturbations of the boundary. These three conditions are satisfied for a known instability induced by the interference of the incident and surface waves (see the works cited above [1]). In our case, the nanorelief is formed due to the deformation of the spalled layer by cavitation bubbles owing to the inhomogeneity of the drag force in the target plane. Cavitation is caused by the tension of the substance in the process of the expansion of a heated target. It is similar to the known phenomenon of the cavitation “spallation” in a liquid despite the large difference between the space-time scales of the usual spallation facility and the femtosecond heating. Owing to this difference, usual cavitation does not leave any morphological trace on the outer free surface of the spalled layer.     

Interaction of short laser pulses with metals at moderate intensities

The developed model including hydrodynamics with electron heat conduction and electron–ion energy exchange, and cavitation breakup of stretched metastable liquid aluminum (Al) is compared with our laser experiments. For the first time the measured and calculated ablation thresholds agree well in both crater depth and fluence.     

Expansion of Photostable Luminescent Radicals by Meta-Substitution

Polychlorinated pyridyldiphenylmethyl radicals having substituents meta to the position bearing the carbon-centered radical (α-carbon) are synthesized. All of them are stable in ambient conditions in solutions and fluorescent in cyclohexane. The fluorescence of the radicals with bromo, phenyl, 4-chlorophenyl, or 2-pyridyl substituents are enhanced in chloroform, while the emission of the radicals with 2-thienyl or 2-furyl substituents are quenched in chloroform. DFT and TD-DFT calculations indicate that the first doublet excited states of the former are locally excited, while the first doublet excited states of the latter are charge transfer states from the π-electron-donating substituent to the accepting radical. The latter also show much higher photostability under 370-nm light irradiation compared with the first reported photostable fluorescent radical, (3,5-dichloro-4-pyridyl)bis(2,4,6-trichlorophenyl)methyl radical (PyBTM), with pronounced bathochromic shifts of the fluorescence.     

Giant Hysteretic Single‐Molecule Electric Polarisation Switching above Room Temperature

Continual progress has been achieved in information technology through unrelenting miniaturisation of the single memory bit in integrated ferromagnetic, ferroelectric, optical, and related circuits. However, as miniaturisation approaches its theoretical limit, new memory materials are being sought. Herein, we report a unique material exhibiting single‐molecule electric polarisation switching that can operate above room temperature. The phenomenon occurs in a Preyssler‐type polyoxometalate (POM) cluster we call a single‐molecule electret (SME). It exhibits all the characteristics of ferroelectricity but without long‐range dipole ordering. The SME affords bi‐stability as a result of the two potential positions of localisation of a Tb³⁺ ion trapped in the POM, resulting in extremely slow relaxation of the polarisation and electric hysteresis with high spontaneous polarisation and coercive electric fields. Our findings suggest that SMEs can potentially be applied to ultrahigh‐density memory 1 and other molecular‐level electronic devices operating above room temperature. 2     

Modification of the luminescence spectra of chloro(tetrapyridylcyclotetramine)europium complexes by fine tuning of the Eu-Cl distance with outer-sphere counterions in the solid state, in a polymer matrix and in solution

Controlling the coordination environments and the luminescence properties of Eu(3+) complexes with outer-sphere counterions was achieved in the solid state, in a polymer matrix and in solution.     

Redox-assisted ring closing reaction of the photogenerated cyclophanediene form of bis(ferrocenyl)dimethyldihydropyrene with interferrocene electronic communication switching

We synthesized ferrocene-attached dimethyldihydropyrene (DHP) derivatives and investigated their photochemical and redox behaviors. For bis(ferrocenylethynyl)dimethyldihydropyrene (1), reversible photoisomerization between the closed DHP form (1c) and the open CPD form (1o) occurred in high yields upon alternate irradiation of visible (578 nm) light and UV (303 nm) light, whereas no photoisomerization proceeded for bis(pentamethylferrocenylethynyl)dimethyldihydropyrene (2). 1 exhibited reversible switching of electronic communication between the ferrocene (Fc) moieties by photoisomerization of the DHP moiety and demonstrated a novel ring closing reaction induced by oxidation of the Fc moieties. The magnitude of electronic communication, deltaE0' (the difference between the redox potentials of two Fc's), was 63 mV in 1c and 16 mV in 1o, indicating that the electronic communication through the spacer is enhanced in the more developed pi-conjugation of the DHP moiety. The rate constants of the ring closing reaction from 1o+ to 1c+ and from 1o2+ to 1c2+ were estimated at 3.7 and 0.50 s(-1), respectively, by the simulation of cyclic voltammograms.     

Realization of SOMO-HOMO level conversion for a TEMPO-dithiolate ligand by coordination to platinum(II)

We developed a TEMPO-bound dithiolate ligand (= tempodt) and its Pt(diimine)(dithiolate) complex to realize a unique electronic structure with the potential for unprecedented functionalities. The physical properties and electronic structures of tempodt, (tempodt)Pt, and their related compounds were investigated by cyclic voltammetry, UV-visible spectroscopy, electron spin resonance (ESR) spectroscopy, and other techniques. It was revealed that (tempodt)Pt showed an unusual electronic structure in which the HOMO level (= pi-conjugated dithiolate-based orbital) was located above the SOMO level attributed to the TEMPO moiety, and that this situation was achieved via a drastic electronic structure change of SOMO-HOMO level conversion through complex formation. These findings were further supported by an investigation into a one-electron oxidized (tempodt)Pt and related complexes.