Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0.68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0.68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Tuning the beta-turn segment in designed peptide beta-hairpins: Construction of a stable type I ' beta-turn nucleus and hairpin-helix transition promoting segments

Designed octapeptides Boc-Leu-Val-Val-Aib-(D)Xxx-Leu- Val-Val-OMe ((D)Xxx = (D)Ala, 3a; (D)Val, 3c and (D)Pro, 5a) and Boc-Leu-Phe-Val-Aib-DAla-Leu-Phe-Val-OMe (3b) have been investigated to construct models of a stable type I' beta-turn nucleated hairpin and to generate systems for investigating helix-hairpin conformational transitions. Peptide 5a, which contains a central Aib-(D)Pro segment, is shown to adopt a stable type I' beta-turn nucleated hairpin structure, stabilized by four cross-strand hydrogen bonds. The stability of the structure in diverse solvents is established by the observation of all diagnostic NOEs expected in a beta-hairpin conformation. Replacement of (D)Pro5 by (D)Ala/(D)Val (3a-c) results in sequences that form beta-hairpins in hydrogen bonding solvents like CD3OH and DMSO-d(6). However, in CDCl3 evidence for population of helical conformations is obtained. Peptide 6b (Boc-Leu-Phe-Val-Aib-Aib-Leu-Phe-Val-OMe), which contains a centrally positioned Aib-Aib segment, provides a clear example of a system, which exhibits a helical conformation in CDCl3 and a significant population of both helices and hairpins in CD3OH and DMSO-d(6). The coexistence of multiple conformations is established by the simultaneous observation of diagnostic NOEs. Control over stereochemistry of the central beta-turn permits generation of models for robust beta-hairpins and also for the construction of systems that may be used to probe helix-hairpin conformational transitions. (c) 2006 Wiley Periodicals, Inc.

Excitation energy transfer from a fluorophore to single-walled carbon nanotubes

We study the process of electronic excitation energy transfer from a fluorophore to the electronic energy levels of a single-walled carbon nanotube. The matrix element for the energy transfer involves the Coulombic interaction between the transition densities on the donor and the acceptor. In the Foumlrster approach, this is approximated as the interaction between the corresponding transition dipoles. For energy transfer from a dye to a nanotube, one can use the dipole approximation for the dye, but not for the nanotube. We have therefore calculated the rate using an approach that avoids the dipole approximation for the nanotube. We find that for the metallic nanotubes, the rate has an exponential dependence if the energy that is to be transferred, h is less than a threshold and a d(-5) dependence otherwise. The threshold is the minimum energy required for a transition other than the k(i,perpendicular to)=0 and l=0 transition. Our numerical evaluation of the rate of energy transfer from the dye pyrene to a (5,5) carbon nanotube, which is metallic leads to a distance of similar to 165 A degrees up to which energy transfer is appreciable. For the case of transfer to semiconducting carbon nanotubes, apart from the process of transfer to the electronic energy levels within the one electron picture, we also consider the possibility of energy transfer to the lowest possible excitonic state. Transfer to semiconducting carbon nanotubes is possible only if>=epsilon(g)-epsilon(b). The long range behavior of the rate of transfer has been found to have a d(-5) dependence if h >=epsilon(g). But, when the emission energy of the fluorophore is in the range epsilon(g)>h >=epsilon(g)-epsilon(b), the rate has an exponential dependence on the distance. For the case of transfer from pyrene to the semiconducting (6,4) carbon nanotube, energy transfer is found to be appreciable up to a distance of similar to 175 A degrees.

Electronic excitations in solids studied using inelastic x-ray scattering

Inelastic x-ray scattering can be used to study the electronic structure of matter. The x rays scattered from the target both induce and carry information on the electronic excitations taking place in the system. These excitations are the manifestations of the electronic structure and the physics governing the many-body system. This work presents results of non-resonant inelastic x-ray scattering experiments on a range of materials including metallic, insulating and semiconducting compounds as well as an organic polymer. The experiments were carried out at the National Synchrotron Light Source, USA and at the European Synchrotron Radiation Facility, France. The momentum transfer dependence of the experimental valence- and core-electron excitation spectra is compared with the results of theoretical first principles computations that incorporate the electron-hole interaction. A recently developed method for analyzing the momentum transfer dependence of core-electron excitation spectra is studied in detail. This method is based on real space multiple scattering calculations and is used to extract the angular symmetry components of the local unoccupied density of final states.

Dimensional Reduction Near the Deconfinement Transition

When ordinary nuclear matter is heated to a high temperature of ~ 10^12 K, it undergoes a deconfinement transition to a new phase, strongly interacting quark-gluon plasma. While the color charged fundamental constituents of the nuclei, the quarks and gluons, are at low temperatures permanently confined inside color neutral hadrons, in the plasma the color degrees of freedom become dominant over nuclear, rather than merely nucleonic, volumes. Quantum Chromodynamics (QCD) is the accepted theory of the strong interactions, and confines quarks and gluons inside hadrons. The theory was formulated in early seventies, but deriving first principles predictions from it still remains a challenge, and novel methods of studying it are needed. One such method is dimensional reduction, in which the high temperature dynamics of static observables of the full four-dimensional theory are described using a simpler three-dimensional effective theory, having only the static modes of the various fields as its degrees of freedom. A perturbatively constructed effective theory is known to provide a good description of the plasma at high temperatures, where asymptotic freedom makes the gauge coupling small. In addition to this, numerical lattice simulations have, however, shown that the perturbatively constructed theory gives a surprisingly good description of the plasma all the way down to temperatures a few times the transition temperature. Near the critical temperature, the effective theory, however, ceases to give a valid description of the physics, since it fails to respect the approximate center symmetry of the full theory. The symmetry plays a key role in the dynamics near the phase transition, and thus one expects that the regime of validity of the dimensionally reduced theories can be significantly extended towards the deconfinement transition by incorporating the center symmetry in them. In the introductory part of the thesis, the status of dimensionally reduced effective theories of high temperature QCD is reviewed, placing emphasis on the phase structure of the theories. In the first research paper included in the thesis, the non-perturbative input required in computing the g^6 term in the weak coupling expansion of the pressure of QCD is computed in the effective theory framework at an arbitrary number of colors. The two last papers on the other hand focus on the construction of the center-symmetric effective theories, and subsequently the first non-perturbative studies of these theories are presented. Non-perturbative lattice simulations of a center-symmetric effective theory for SU(2) Yang-Mills theory show --- in sharp contrast to the perturbative setup --- that the effective theory accommodates a phase transition in the correct universality class of the full theory. This transition is seen to take place at a value of the effective theory coupling constant that is consistent with the full theory coupling at the critical temperature.

Dynamo onset as a first-order transition: Lessons from a shell model for magnetohydrodynamics

We carry out systematic and high-resolution studies of dynamo action in a shell model for magnetohydro-dynamic (MHD) turbulence over wide ranges of the magnetic Prandtl number Pr-M and the magnetic Reynolds number Re-M. Our study suggests that it is natural to think of dynamo onset as a nonequilibrium first-order phase transition between two different turbulent, but statistically steady, states. The ratio of the magnetic and kinetic energies is a convenient order parameter for this transition. By using this order parameter, we obtain the stability diagram (or nonequilibrium phase diagram) for dynamo formation in our MHD shell model in the (Pr-M(-1), Re-M) plane. The dynamo boundary, which separates dynamo and no-dynamo regions, appears to have a fractal character. We obtain a hysteretic behavior of the order parameter across this boundary and suggestions of nucleation-type phenomena.

Radiation effects in supported nanoparticles

Nanotechnology applications are entering the market in increasing numbers, nanoparticles being among the main classes of materials used. Particles can be used, e.g., for catalysing chemical reactions, such as is done in car exhaust catalysts today. They can also modify the optical and electronic properties of materials or be used as building blocks for thin film coatings on a variety of surfaces. To develop materials for specific applications, an intricate control of the particle properties, structure, size and shape is required. All these depend on a multitude of factors from methods of synthesis and deposition to post-processing. This thesis addresses the control of nanoparticle structure by low-energy cluster beam deposition and post-synthesis ion irradiation. Cluster deposition in high vacuum offers a method for obtaining precisely controlled cluster-assembled materials with minimal contamination. Due to the clusters small size, however, the cluster-surface interaction may drastically change the cluster properties on deposition. In this thesis, the deposition process of metal and alloy clusters on metallic surfaces is modelled using molecular dynamics simulations, and the mechanisms influencing cluster structure are identified. Two mechanisms, mechanical melting upon deposition and thermally activated dislocation motion, are shown to determine whether a deposited cluster will align epitaxially with its support. The semiconductor industry has used ion irradiation as a tool to modify material properties for decades. Irradiation can be used for doping, patterning surfaces, and inducing chemical ordering in alloys, just to give a few examples. The irradiation response of nanoparticles has, however, remained an almost uncharted territory. Although irradiation effects in nanoparticles embedded inside solid matrices have been studied, almost no work has been done on supported particles. In this thesis, the response of supported nanoparticles is studied systematically for heavy and light ion irradiation. The processes leading to damage production are identified and models are developed for both types of irradiation. In recent experiments, helium irradiation has been shown to induce a phase transformation from multiply twinned to single-crystalline nanoparticles in bimetallic alloys, but the nature of the transition has remained unknown. The alloys for which the effect has been observed are CuAu and FePt. It is shown in this thesis that transient amorphization leads to the observed transition and that while CuAu and FePt do not amorphize upon irradiation in bulk or as thin films, they readily do so as nanoparticles. This is the first time such an effect is demonstrated with supported particles, not embedded in a matrix where mixing is always an issue. An understanding of the above physical processes is essential, if nanoparticles are to be used in applications in an optimal way. This thesis clarifies the mechanisms which control particle morphology, and paves way for the synthesis of nanostructured materials tailored for specific applications.

Nickel(II) meso-hydroxyporphyrin complexes revisited: Palladium-catalysed synthesis, electronic structures of derived oxy radicals, and oxidative coupling to a dioxoporphodimethene dyad

We report the synthesis and characterisation of new examples of meso-hydroxynickel(II) porphyrins with 5,15-diphenyl and 10-phenyl-5,15-diphenyl/diaryl substitu- tion. The OH group was introduced by using carbonate or hydroxide as nucleophile by using palladium/phosphine cat- alysis. The NiPor OHs exist in solution in equilibrium with the corresponding oxy radicals NiPor OC. The 15-phenyl group stabilises the radicals, so that the 1H NMR spectra of {NiPor OH} are extremely broad due to chemical exchange with the paramagnetic species. The radical concentration for the diphenylporphyrin analogue is only 1%, and its NMR line-broadening was able to be studied by variable-tempera- ture NMR spectroscopy. The EPR signals of NiPor OC are con- sistent with somewhat delocalised porphyrinyloxy radicals, and the spin distributions calculated by using density func- tional theory match the EPR and NMR spectroscopic obser- vations. Nickel(II) meso-hydroxy-10,20-diphenylporphyrin was oxidatively coupled to a dioxo-terminated porphodimethene dyad, the strongly red-shifted electronic spectrum of which was successfully modelled by using time-dependent DFT calculations.

Monoclinic polymorph of Boc-Trp-Ile-Ala-Aib-Ile-Val-Aib-Leu-Aib-Pro-OMe(anhydrous). Parallel packing of 3(10)-/alpha-helices and a transition of helix type

The structures of two crystal forms of Boc-Trp-Ile-Ala-Aib-Ile-Val-Aib-Leu-Aib-Pro-OMe have been determined. The triclinic form (P1, Z = 1) from DMSO/H2O crystallizes as a dihydrate (Karle, Sukumar & Balaram (1986) Proc, Natl, Acad. Sci. USA 83, 9284-9288). The monoclinic form (P2(1), Z = 2) crystallized from dioxane is anhydrous. The conformation of the peptide is essentially the same in both crystal system, but small changes in conformational angles are associated with a shift of the helix from a predominantly alpha-type to a predominantly 3(10)-type. The r.m.s. deviation of 33 atoms in the backbone and C beta positions of residues 2-8 is only 0.29 A between molecules in the two polymorphs. In both space groups, the helical molecules pack in a parallel fashion, rather than antiparallel. The only intermolecular hydrogen bonding is head-to-tail between helices. There are no lateral hydrogen bonds. In the P2(1) cell, a = 9.422(2) A, b = 36.392(11) A, c = 10.548(2) A, beta = 111.31(2) degrees and V = 3369.3 A for 2 molecules of C60H97N11O13 per cell.

Scanning Tunneling Spectroscopy on Pr0.68Pb0.32MnO3 single crystals

Scanning tunneling microscopy/spectroscopy studies were carried out on single crystals of colossal magnetoresistive manganite Pr0. 68Pb0.32MnO3 at different temperatures in order to probe their spatial homogeneity across the metal-insulator transition temperature TM-I(similar to 255 K). A metallic behavior of the local conductance was observed for temperatures T < TM-I. Zero bias conductance (dI/dV)v=(0), which is directly proportional to the local surface density of states at the Fermi level, shows a single distribution at temperatures T < 200 K suggesting a homogeneous electronic phase at low temperatures. In a narrow temperature window of 200 K < T < TM-I, however, an inhomogeneous distribution of (dI/dV)v=(0) has been observed. This result gives evidence for phase separation in the transition region in this compound.

Electronic structure and bonding of beta-rhombohedral boron using cluster fragment approach

Theoretical studies using density functional theory are carried out to understand the electronic structure and bonding and electronic properties of elemental beta-rhombohedral boron. The calculated band structure of ideal beta-rhombohedral boron (B-105) shows valence electron deficiency and depicts metallic behavior. This is in contrast to the experimental result that it is a semiconductor. To understand this ambiguity we discuss the electronic structure and bonding of this allotrope with cluster fragment approach using our recently proposed mno rule. This helps us to comprehend in greater detail the structure of B-105 and materials which are closely related to beta-rhombohedral boron. The molecular structures B12H12-2, B28H21+1, BeB27H21, LiB27H21-1, CB27H21+2, B57H36+3, Be3B54H36, and Li2CB54H36, and corresponding solids Li8Be3B102 and Li10CB102 are arrived at using these ideas and studied using first principles density functional theory calculations.

Retirement Transition and Well-being : A 16-year Longitudinal Study

The ageing of the labour force and falling employment rates have forced policy makers in industrialized countries to find means of increasing the well-being of older workers and of lengthening their work careers. The main objective of this thesis was to study longitudinally how health, functional capacity, subjective well-being, and lifestyle change as people grow older, and what effect retirement has on these factors and on their relationships. The present study is a follow-up questionnaire study of Finnish municipal workers, conducted in 1981 to 1997 at the Finnish Institute of Occupational Health. In 1981, a postal questionnaire was sent to 7344 municipal workers in different parts of Finland. The respondents were born between 1923 and 1937. A total of 6257 persons responded to the first questionnaire. In the end, a total of 3817 persons had responded to all four (1981, 1985, 1992, 1997) questionnaires. (The response rate was 69% of the living participants). Cross-tabulations, comparison of means, logistic regression analyses and general linear models with repeated measures were used to derive the results. The transition from work life to retirement, and the following years as a pensioner were associated with many changes. Involvement in various activities increased during the transition stage but later decreased to the previous level. Physical exercise was an exception: it became increasingly popular over the years. Perceived health improved markedly from the working stage to the retirement transition stage, even though morbidity increased steadily during the follow-up. On the other hand, functional capacity decreased over the follow-up, especially among those who were occupationally active until the retirement stage. Subjective well-being remained stable during the follow-up period. There were, however, great differences based on the type of work, favouring those whose work had been mental in nature. The impact of activity level on maintaining well-being became greater during the follow-up, whereas the effect of physical functioning diminished. Good physical functioning and an active life-style contributed to staying on at work until normal retirement age. Also work-related factors, i.e. possibilities for development and influence at work, responsibility for others, meaningful work, and satisfaction with working time arrangements were positively related to continuing working. The transition from work to retirement had a positive impact on a person s health and functional capacity. The study results support the view that it should be possible to ease one s work pace during the last years of a work career. This might lower the threshold between work and retirement and convince people that there will still be time to enjoy retirement also a few years later.