Mechanism of plasma-initiated polymerization: Concerning the nature of solvent effects on the lifelike polymerization of water-soluble vinyl monomers

To provide a satisfactory basic understanding of the solvent effect of plasma-initiated polymerization, we have carried out several kinds of polymerizations of various water-soluble vinyl monomers. It has been shown that aqueous solution of such vinyl monomers underwent the polymerizations induced by methyl isobutyrate (MIB) plasma-exposed glass surface. The invisible ultrathin polymer film trapping an active radical species deposited on the plasma-exposed glass surface apparently induced the polymerizations. The efficiency, however, was largely dependent on the solvent used: the solvent can be considered to act as “an initiation-activator” for the lifelike postpolymerization. The nature of the solvent effect was ascribed to the physicomechanical property such as swelling ability and/or solubility toward the ultrathin film formed on the glass surface. Thus it has been suggested that the choice of good-balanced combination between the structural feature of the plasma-induced ultrathin polymer film and the solvent as an initiation-activator is important to achieve activity of a desired solution polymerization.     

Synthesis and properties of p-benzoquinone-fused hexadehydro[18]annulenes

A series of hexadehydro[18]annulenes fused with different numbers of p-benzoquinone, 4-6, were synthesized by stepwise transformation of the p-dimethoxybenzene moiety of the precursor dehydroannulene 3 fused with three 3,6-dimethoxy-4,5-dimethylbenzene units at 1,2-positions into p-benzoquinone using ceric ammonium nitrate. The UV-vis spectra of compounds 4 and 5, which have both electron-donating p-dimethoxybenzene unit(s) and electron-accepting p-benzoquinone unit(s) in the π-systems, showed the maximum absorption bands bathochromically shifted in comparison with 3 having only p-dimethoxybenzene units and 6 having only p-benzoquinone units. However, the solvatochromism expected for 4 and 5 was found to be quite weak possibly because the HOMO and LUMO (B3LYP/6-31G(d)) are not localized but rather delocalized over the whole π-systems.     

Photo-induced dimerization of 1-naphthoxide anion: Electron transfer mechanism

Irradiation of sodium 1-naphthoxide in MeOH gave selectively 1,4-dihydro-4',8-dihydroxy-1,1'-binaphthyl 2. A similar reaction in PhH afforded the regioisomer 5, along with 6, Structural proof is presented for these hitherto unknown dimers. The reaction is completely quenched in the presence of naphthalene, a good electron scavenger. This new type of photodimerization was proved to be initiated by intermolecular electron-transfer from the excited 1-naphthoxide anion to the ground state one to give the oxidation-reduction dimers.     

Mechanism of external heavy-atom enhancement of the radiative transition rate from the π,π* triplet state

The effect of external heavy-atom perturbation is examined for each of the three spin subcomponents of the π,π^* triplet state. It is shown that the radiative decay rate from the subcomponent whose spin wavefunction is within the molecular plane is most effectively enhanced. The main perturbing singlet state is the charge-transfer state arising from the excitation of an electron from a π orbital of the molecule to the σ^* orbital of the perturber.     

Electron spin resonance of the two-dimensional metallic state and the quantum Hall state in a Si/SiGe quantum well

We report electrically detected electron spin resonance (ESR) measurements of a high mobility two-dimensional (2D) electron system formed in a Si/SiGe quantum well, with millimeter wave in a high magnetic field . The negative ESR signal observed under an in-plane magnetic field gives direct evidence that the spin polarization leads to a resistance increase in the 2D metallic state. Suppression of spin decoherence was observed in the quantum Hall state at the Landau level filling factor ν=2. Strength of the nuclear magnetic field in the resonance is evaluated to be less than , much smaller than that reported for GaAs/AlGaAs heterostructures.     

Permutation complexity via duality between values and orderings

We study the permutation complexity of finite-state stationary stochastic processes based on a duality between values and orderings between values. First, we establish a duality between the set of all words of a fixed length and the set of all permutations of the same length. Second, on this basis, we give an elementary alternative proof of the equality between the permutation entropy rate and the entropy rate for a finite-state stationary stochastic processes first proved in [J.M. Amigó, M.B. Kennel, L. Kocarev, The permutation entropy rate equals the metric entropy rate for ergodic information sources and ergodic dynamical systems, Physica D 210 (2005) 77-95]. Third, we show that further information on the relationship between the structure of values and the structure of orderings for finite-state stationary stochastic processes beyond the entropy rate can be obtained from the established duality. In particular, we prove that the permutation excess entropy is equal to the excess entropy, which is a measure of global correlation present in a stationary stochastic process, for finite-state stationary ergodic Markov processes.     

Spectral Gap and Exponential Decay of Correlations

We study the relation between the spectral gap above the ground state and the decay of the correlations in the ground state in quantum spin and fermion systems with short-range interactions on a wide class of lattices. We prove that, if two observables anticommute with each other at large distance, then the nonvanishing spectral gap implies exponential decay of the corresponding correlation. When two observables commute with each other at large distance, the connected correlation function decays exponentially under the gap assumption. If the observables behave as a vector under the U(1) rotation of a global symmetry of the system, we use previous results on the large distance decay of the correlation function to show the stronger statement that the correlation function itself, rather than just the connected correlation function, decays exponentially under the gap assumption on a lattice with a certain self-similarity in (fractal) dimensions D < 2. In particular, if the system is translationally invariant in one of the spatial directions, then this self-similarity condition is automatically satisfied. We also treat systems with long-range, power-law decaying interactions.     

Time decay of solutions to the cauchy problem for time-dependent Schrödinger-Hartree equations

We consider the time-dependent Schrödinger-Hartree equation (1) $$iu_t + \Delta u = \left( {\frac{1}{r}*|u|^2 } \right)u + \lambda \frac{u}{r},(t, x) \in \mathbb{R} \times \mathbb{R}^3 ,$$ (2) $$u(0,x) = \phi (x) \in \Sigma ^{2,2} ,x \in \mathbb{R}^3 ,$$ where λ≧0 and \(\Sigma ^{2,2} = \{ g \in L^2 ;\parallel g\parallel _{\Sigma ^{2,2} }^2 = \sum\limits_{|a| \leqq 2} {\parallel D^a g\parallel _2^2 + \sum\limits_{|\beta | \leqq 2} {\parallel x^\beta g\parallel _2^2< \infty } } \} \) . We show that there exists a unique global solutionu of (1) and (2) such that $$u \in C(\mathbb{R};H^{1,2} ) \cap L^\infty (\mathbb{R};H^{2,2} ) \cap L_{loc}^\infty (\mathbb{R};\Sigma ^{2,2} )$$ with $$u \in L^\infty (\mathbb{R};L^2 ).$$ Furthermore, we show thatu has the following estimates: $$\parallel u(t)\parallel _{2,2} \leqq C,a.c. t \in \mathbb{R},$$ and $$\parallel u(t)\parallel _\infty \leqq C(1 + |t|)^{ - 1/2} ,a.e. t \in \mathbb{R}.$$      

Stroboscopic phase portrait and strange attractors

External periodic modulation of a nonlinear oscillator may lead to a chaotic output behaviour. This phenomenon is attributed to the existence of a strange attractor, which embodies essentially a folding motion as is met in Bernoulli shift or the Baker's transformation.