Melting and unzipping of DNA

Existing experimental studies of the thermal denaturation of DNA yield sharp steps in the melting curve suggesting that the melting transition is first order. This transition has been theoretically studied since the early sixties, mostly within an approach in which the microscopic configurations of a DNA molecule consist of an alternating sequence of non-interacting bound segments and denaturated loops. Studies of these models neglect the repulsive, self-avoiding, interaction between different loops and segments and have invariably yielded continuous denaturation transitions. In the present study we take into account in an approximate way the excluded-volume interaction between denaturated loops and the rest of the chain. This is done by exploiting recent results on scaling properties of polymer networks of arbitrary topology. We also ignore the heterogeneity of the polymer. We obtain a first-order melting transition in d = 2 dimensions and above, consistent with the experimental results. We also consider within our approach the unzipping transition, which takes place when the two DNA strands are pulled apart by an external force acting on one end. We find that the under equilibrium condition the unzipping transition is also first order. Although the denaturation and unzipping transitions are thermodynamically first order, they do exhibit critical fluctuations in some of their properties. For instance, the loop size distribution decays algebraically at the transition and the length of the denaturated end segment diverges as the transition is approached. We evaluate these critical properties within our approach. Received 21 August 2001 and Received in final form 26 January 2002     

Manifestation of Extracoordination in the Resonance Raman Spectra of Water‐Soluble Cation Co‐Porphyrins

Resonance Raman spectra (RRS) of Co(II) and Co(III)5,10,15,20tetrakis(4Nmethylpyridinium)porphyrin ((Co^II(TmpyP4), and Co^III(TMPyP4)) in aqueous solutions at different pH as well as in organic solvents (methanol, ethanol, DMSO, DMF) are obtained. The increased sensitivity of the oscillation frequencies ₂, ₄, ₈, and ₆ — the markers of the oxidation state of a metal — to the nature of an axial ligand has been revealed. For Co^III(TmpyP4), the shifts of the indicated frequencies in extracoordination have turned out to be twofold larger than those for Co^II(TmpyP4). The spectral effects observed are related to different electron influence of the extraligands on the system of the porphyrin ring. In the case of Co(III)porphyrin, interaction of the d orbitals of the metal and the e _g ^*orbitals of the macrocycle is more efficient since its ionic radius is smaller than for the Co(II)complex. For Co^III(TmpyP4), a linear correlation between the oscillation frequencies ₂, ₄, ₈, and ₆ and the experimental Gutmann parameters characterizing the electronacceptor properties of solvents is found.     

Mössbauer Study of Oxygenated Iron-Phthalocyanines,a Precursor of Magnetic Storage Material

⁵⁷Fe transmission Mössbauer spectroscopy and X-ray diffractometry were used to study - and -polymorphs of iron phthalocyanines (FePc) to get information about their oxygenation in connection with controlled pyrolysis of flat layered phthalocyanines initiated by radicals at relatively low temperatures, to form acicular carbide particles encaged in carbon. Mössbauer spectroscopy and XRD revealed that the oxygenation of both - and -polymorphs of FePc was successfully achieved. New Mössbauer spectral components (doublets) appeared upon the oxygenation in both and FePc. This can be attributed to iron microenvironments containing oxygen between the layers of iron phthalocyanines.     

Birefringence imaging of human skin by polarization-sensitive spectral interferometric optical coherence tomography

We have developed a spectral interferometric optical coherence tomography (OCT) system with polarization sensitivity that is able to measure a two-dimensional tomographic image by means of one-dimensional mechanical scanning. Our system, which has an axial resolution of 32 mum , calculates the distribution of each element of the Müller matrix of a measured object from 16 OCT images. The OCT system successfully reveals the birefringent nature of human skin tissue.     

IR-poled second-harmonic generation in glass

Infrared (IR)-induced second-harmonic generation in the chalcogenide glasses is observed. A phenomenological approach of IR picosecond non-linear optical (NLO) response in glass is developed for the middle IR spectral range (5–15 μm). The observed effect is explained within the framework of fifth-order NLO susceptibilities. A model that reproduces the basic characteristics of the experimental data, in which the optical non-linearities caused by photoinduced electron–phonon anharmonic interactions, is proposed. The role of the IR-induced phase matching conditions in the observed phenomenon is discussed.     

Multiple scattering of fractionally charged quasiparticles

We employ shot noise measurements to characterize the effective charge of quasiparticles, at filling factor nu=1/3 of the fractional quantum Hall regime, as they scatter from an array of identical weak backscatterers. Upon scattering, quasiparticles are known to bunch, e.g., only three e/3 charges, or "electrons" are found to traverse a rather opaque potential barrier. We find here that the effective charge scattered by an array of scatterers is determined by the scattering strength of an individual scatterer and not by the combined scattering strength of the array, which can be very small. Moreover, we also rule out intraedge equilibration of e/3 quasiparticles over a length scale of hundreds of microns.     

Electron-hole coupling and the charge density wave transition in TiSe2

Angle-resolved photoemission is employed to measure the band structure of TiSe2 in order to clarify the nature of the ( 2 x 2 x 2) charge density wave transition. The results show a very small indirect gap in the normal phase transforming into a larger indirect gap at a different location in the Brillouin zone. Fermi surface topology is irrelevant in this case. Instead, electron-hole coupling together with a novel indirect Jahn-Teller effect drives the transition.     

Origin of the stability of Ge(105) on si: a new structure model and surface strain relaxation

The structure of Ge(105)-(1 x 2) grown on Si(105) is examined by scanning tunneling microscopy (STM) and first-principles calculations. The morphology evolution with an increasing amount of Ge deposited documents the existence of a tensile surface strain in Si(105) and its relaxation with increasing coverage of Ge. A detailed analysis of high-resolution STM images and first-principles calculations produce a new stable model for the Ge(105)-(1 x 2) structure formed on the Si(105) surface that includes the existence of surface strain. It corrects the model developed from early observations of the facets of "hut" clusters grown on Si(001).     

Energetics and vibrational states for hydrogen on Pt(111)

We present a combination of theoretical calculations and experiments for the low-lying vibrational excitations of H and D atoms adsorbed on the Pt(111) surface. The vibrational band states are calculated based on the full three-dimensional adiabatic potential energy surface obtained from first-principles calculations. For coverages less than three quarters of a monolayer, the observed experimental high-resolution electron peaks at 31 and 68 meV are in excellent agreement with the theoretical transitions between selected bands. Our results convincingly demonstrate the need to go beyond the local harmonic oscillator picture to understand the dynamics of this system.