Solvent dependence of the ultrafast ground state recovery dynamics of phenol blue

We have studied femtosecond ground state recovery dynamics of phenol blue (PB) by pump-probe spectroscopy with a time resolution of 33 fs. Multiexponential decay with time constants extending from 300 fs to 10 ps were observed. Some low frequency intramolecular quantum beats were also observed. Solvent dependence of these decays and beats are discussed.     

Appearance of pseudo-band-gaps in a disordered quantum wire array

The density of states and the conductivity are calculated in lateral superlattices with disorder in the period within a self-consistent Born approximation. Although the potential loses its periodicity on average due to disorder, it leads to an opening up of a pseudo-band-gap and modifies the conductivity perpendicular to the superlattice even qualitatively, when the energy reaches the zone boundary.     

Nonlinear response in evaluating the subjective diffuseness of sound fields

Tests were conducted to determine which horizontal reflection angles are most effective in stimulating subjective diffuseness for a listener in a room. Paired comparison tests were carried out where subjects were asked to judge in which of two sound fields they perceived more diffuseness. Results show that the most effective horizontal angle depends on the frequency of the one-third-octave-band noise, as is indicated by the interaural cross correlation. The remarkable finding in this investigation is that the scale value of subjective diffuseness may be formulated in terms of the 3/2 power of the magnitude of interaural cross correlation (IACC) and that the scale value does not vary with the frequency of the bandpass noise source.     

Extreme point axioms for closure spaces

A pair (X,τ) of a finite set X and a closure operator τ:2^X→2^X is called a closure space. The class of closure spaces includes matroids as well as antimatroids. Associated with a closure space (X,τ), the extreme point operator ex:2^X→2^X is defined as ex(A)={p|p∈A,p∉τ(A-{p})}. We give characterizations of extreme point operators of closure spaces, matroids and antimatroids, respectively.     

The axial methionine ligand may control the redox reorganizations in the active site of blue copper proteins

Structural and energetic reorganizations in redox reaction of type 1 copper proteins are studied by density functional and ab initio molecular orbital calculations. Model complexes of the active site with varying number of ligands, from Cu(SCH(3))(0/+) to Cu(SCH(3))(Im)(2)(S(CH(3))(2))(0/+), where Im denotes imidazole, are investigated. Following the findings of structural instability in Cu(I)(SCH(3))(Im)(2) and its stabilization by the addition of the axial methionine (Met) ligand model, the structure and energetics are examined as functions of the Cu-S(Met) distance in the range of 2.1-3.3 A?. The reorganization energies in both redox states exhibit a minimum at the Cu-S(Met) distance of ～2.4?A?, whereas the ionization potential increases monotonically. The changes of reorganization energies correlate well with one of the Cu-N(His) distances rather than the Cu-S(Cys) distance. The estimated Arrhenius factor for oxidation of plastocyanin by P700(+) (in photosystem I) changes by an order of magnitude when the Cu-S(Met) distance fluctuates between 2.4 and 3.0 A?, whereas the factor for reduction of plastocyanin by cytochrome f is nearly constant. Together with the data from our previous classical molecular dynamics simulation of solvated protein, we argue that the electron transfer rate is affected, and thus may be controlled, by the fluctuation of a weakly bound axial Met ligand. We also present the assessment of various exchange-correlation functionals, including those with the long-range correction, against the CCSD(T) reference and on the basis of a perturbative adiabatic connection model. For Cu(SCH(3)) and Cu(SCH(3))(Im), simple correlations have been found between the reorganization energies and the amount of Hartree-Fock exchange.     

Crystallization efficiencies of inorganic polyphosphate oligomers reacted with magnesium and calcium cations using anion-exchange chromatography with particulate formation-laser scattering detector

A particulate formation-laser scattering detector (PFLSD) was developed and used for evaluating the crystallization efficiency of inorganic polyphosphates (PPs) that reacted with either magnesium or calcium cations. As the solutions for reactive crystallization, 0.5 M ammonium buffer (pH 9.6) containing either 0.15 M MgCl₂ or 0.15 M CaCl₂ (MAP: magnesium ammonium phosphate and HAP: hydroxyapatite solution) were used. In the case of mono- and diphosphate (P1 and P2), the significant dependences of the particulate formation efficiency on various types of both P1/P2 and MAP/HAP reaction solutions were observed with the direct sample injection mode. The PFLSD was hyphenated with the anion-exchange chromatography and the dependence of the particulate formation efficiency on the polymerization degree (n_p) of PP oligomers, separated chromatographically, was evaluated sequentially. The significant suppression of the particulate formation for PP oligomers was clearly confirmed, i.e., the MAP and HAP reaction solutions did not produce the particulates of the PP oligomers having an n_p value of more than 3 and 5, respectively. As the overall tendency, the particulate formation efficiency in the case of the HAP solution was superior to that in the case of the MAP solution.     

Persistent hole-burning of perylene microcrystallites dispersed in PVA

A persistent hole-burning is observed in β-perylene microcrystallites, which were embedded in poly-vinyl alcohol. By laser light excitation at 22,535 cm⁻¹ and at 10 K, the hole is found at the excitation photon energy. The mechanism of the persistent hole-burning is interpreted in terms of the resolution of microcrystallites into smaller microcrystallites. This is a novel observation of the persistent hole-burning in aromatic microcrystallites. When the specimen, which includes a hole, is annealed at high temperatures, the resolved microcrystallites restore back to the old position as had been. The β-perylene microcrystallite specimen that we have grown was as small as 1.5 nm in average diameter. They are one order smaller in number of molecules included, compared to those that have been reported on aromatic microcrystallites, anthracene for example. Due to this, we were able to observe the 0-0 transition energy, which varied according as the number of molecules involved in the microcrystallites. We also observed the 0-0 absorption (excitation) spectrum, which depends on the molecular arrays in the microcrystallites. The 0-0 transition of a single molecule in poly-vinyl alcohol matrix is anticipated to be located at 22,885 cm⁻¹.     

Long-lived ultrafast spin precession in manganese alloys films with a large perpendicular magnetic anisotropy

Spin precession with frequencies up to 280 GHz is observed in Mn(3-δ)Ga alloy films with a perpendicular magnetic anisotropy constant K(u)～15 M?erg/cm(3). The damping constant α, characterizing macroscopic spin relaxation and being a key factor in spin-transfer-torque systems, is not larger than 0.008 (0.015) for the δ=1.46 (0.88) film. Those are about one-tenth of α values for known materials with large K(u). First-principles calculations well describe both low α and large K(u) for these alloys.     

Topological Superconductivity in Cu(x)Bi(2)Se(3)

A topological superconductor (TSC) is characterized by the topologically protected gapless surface state that is essentially an Andreev bound state consisting of Majorana fermions. While a TSC has not yet been discovered, the doped topological insulator Cu(x)Bi(2)Se(3), which superconducts below ～3 K, has been predicted to possess a topological superconducting state. We report that the point-contact spectra on the cleaved surface of superconducting Cu(x)Bi(2)Se(3) present a zero-bias conductance peak (ZBCP) which signifies unconventional superconductivity. Theoretical considerations of all possible superconducting states help us conclude that this ZBCP is due to Majorana fermions and gives evidence for a topological superconductivity in Cu(x)Bi(2)Se(3). In addition, we found an unusual pseudogap that develops below ～20 K and coexists with the topological superconducting state.     

Singular orbital magnetism of graphene

The origin of the singular diamagnetic susceptibility at the Dirac point is probed through the study of effects of band-gap opening and spatially varying magnetic field. In the presence of a band gap, the susceptibility is nonzero only inside the band gap and exhibits a discrete jump at the band edges down to zero in the conduction and valence bands. The jump height is understood in terms of the pseudo-spin paramagnetism arising from valley degree of freedom. In spatially varying magnetic field with wave vector q, the susceptibility becomes nonzero only in a finite energy region containing the Dirac point, determined by q. This behavior is understood in terms of electronic states numerically calculated in periodic magnetic field.