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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 4242-4247 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the magnetic circular dichroism (MCD) of exciton states near the band edge of CdSe nanocrystallites (quantum dots). The experiment probes the difference between left and right circularly polarized transitions in the presence of an external magnetic field. Analysis of the MCD signal determines the sign and magnitude of the exciton g-factor which is shown to be highly sensitive to the energy band parameters used in the effective mass approximation. The observation of theoretically predicted changes in the sign of the exciton g-factor between the first two transitions is in agreement with recent theory describing the presence of fine structure underlying the optical transitions of CdSe nanocrystallites. © 1998 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 106 (1997), S. 9869-9882 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the luminescence of surface modified CdSe nanocrystallites. There has been much speculation as to the origin of the band edge emission in these quantum confined structures. Because of their large surface to volume ratios it has been suggested that the emission originates from surface-related states. However, recent theory suggests that the band edge luminescence arises from an optically inactive fine structure state or "dark" exciton. To address this issue we modify the surface of CdSe nanocrystallites with a variety of organic and inorganic ligands. We then monitor the effect changing the surface has on the energetics of the band edge luminescence through photoluminescence and fluorescence line narrowing experiments. Our results are compared with theoretical predictions for the nonresonant and resonant luminescence. We find good agreement between experiment and theory for CdSe nanocrystallites passivated with trioctylphosphine oxide, ZnS, 4-picoline, 4-(trifluoromethyl)thiophenol, and tris(2-ethylhexyl)phosphate. The lack of dependence of our data on surface modification is consistent with a dark exciton description of the band edge luminescence. © 1997 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 9890-9896 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We use x-ray scattering at small angles (SAXS) to study interparticle interactions in dilute dispersions of CdSe nanocrystallite particles. In particular, we probe the dependence of these interactions on a few key parameters, including the nature of the cap molecules attached to the surface of the particles and the solvent. Alkyl capped nanocrystallites with relatively long hydrocarbon chains are stable in a range of solvents. Nanocrystallites capped with smaller molecules show attractive interparticle interactions. Existence of association (e.g., dimers and trimers) in dispersions characterized by attractive interactions is observed in the scattering data for pyridine capped particles. © 1996 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 19 (1986), S. 2770-2778 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 5534-5540 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We generalize a lattice field theory that formally provides an exact description of the statistical mechanical entropy of nonoverlapping flexible polymers to enable treatment of nearest-neighbor interaction energies. The theory is explicitly solved within an extended mean field approximation for a system of polymer chains and voids, and we also provide mean field results for polymer–solvent–void and binary blend–void mixtures. In addition to recovering the Flory–Huggins mean field approximation for these systems, our extended definition of the mean field approximation contains a set of corrections to Flory–Huggins theory in the form of an expansion in powers of the nearest-neighbor interaction energies.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 7272-7284 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An exact field theory is presented to describe a system of self-avoiding lattice polymer chains with arbitrary regularly branched architecture. Equivalently, the chains can be viewed as linear and as composed of structural units (monomers) having a chosen shape and size and therefore each occupying more than one lattice site. The mean field approximation coincides with Flory's theory, and it does not distinguish among chain geometries. However, we develop a systematic expansion for corrections to mean field approximation in powers of z−1 where z is the lattice coordination number. The entropy per site, the pressure and the chain insertion probability are computed for various chain architectures to O(z−2). At equal lattice site coverages per chain and total polymer volume fraction, the more compact the polymer chain geometry the higher is the insertion probability.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 3720-3730 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We introduce a spin field theory for many self- and mutually avoiding polymers with arbitrary stiffness on a regular lattice. The model allows for the complete crossover between flexible polymers and rods. The model also includes arbitrary polymer length distributions and arbitrary volume fractions from the highly dilute regime to the melt. The mean field approximation to the full theory reproduces Flory theory, but our model permits a rigorous and systematic evaluation of corrections to the mean field approximation. The corrections are in the form of a double expansion in powers of the volume fraction ψ and, formally, in powers of the inverse lattice coordination number z−1. We present the correction to first order in z−1 and discuss its relevance to the entropic contribution to the Flory χ parameter for semiflexible polymers.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 3007-3022 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We introduce a lattice spin field theory which formally provides an exact description of the statistics of nonoverlapping, nonintersecting rods on regular lattices. The theory is applicable to arbitrary rod length distributions and arbitrary volume fractions. The mean field approximation reproduces Flory–Huggins theory for rods on a strict lattice, but our theory permits the rigorous and systematic evaluation of corrections to the mean field entropies. We present those corrections as a cluster expansion for the entropy density which involves a double expansion in powers of the volume fraction ψ and the inverse of the lattice coordination number z−1. Our results are compared for specific cases with those of DiMarzio's theory which is more accurate than mean field. For dimers which are equally distributed among the possible lattice directions of a hypercubic lattice, we find very good agreement between our theory and DiMarzio's with ours giving a slightly larger entropy density when corrections to mean field to order ψ4 are included. Through order ψ3, our entropy for longer rods is identical to that of DiMarzio's expanded similarly. Our dimer results, however, demonstrate that the ψ4 term for rods contains contributions which we attribute to locally ordered configurations and which are absent in DiMarzio's theory. Our results are compared with the exact entropy density for dimers fully covering an infinite square planar lattice; the inclusion of corrections to mean field up to order z−2 narrows the error from 33.8% for mean field to 7.85%. Our theory, however, also describes the dimer–monomer problem which has not been very amenable to analytic theories.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 7036-7047 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We continue the analysis of the lattice spin-field theory which is introduced in paper I and which formally gives the exact entropy for a set of completely flexible self-avoiding polymers on a lattice. The model allows for arbitrary chain length distributions and arbitrary polymer volume fractions. Use of random fields produces a field theory from which Flory–Huggins results are recovered in the mean field limit. Here we recast the mean field formulation to allow for the rigorous and systematic evaluation of corrections by means of a cluster expansion. We then calculate corrections to the mean field directly up to fourth order and provide a systematic diagrammatic method for evaluating general order corrections. Our results illustrate the polymer concentration dependence of the corrections to the Flory–Huggins mean field results as well as provide the origins for the entropic contribution to the Flory χ parameter and its concentration dependence. Generalizations to treat rods and semiflexible polymers will be given elsewhere.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 84 (1986), S. 449-464 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A theoretical description of excluded volume in polyelectrolytes is considered in the flexible chain limit. The approach generalizes the work of Kholodenko and Freed and removes some deficiencies, present in their work, which become apparent in further extensions of the theory. Renormalization group calculations are pursued to order ε=4−d for the mean square end-to-end distance 〈R2〉, the radius of gyration 〈S2〉, and the second virial coefficient A2. The importance of including both a short range excluded volume interaction as well as a long range electrostatic one is stressed. The electrostatic interaction is effectively treated as a perturbation, so that the results are valid only in the weak electrostatic coupling region. The theory shows that polyelectrolyte excluded volume effects cannot generally be described in a scaling limit, and generalized scaling laws are derived which contain several parameters including the two interaction parameters. A qualitative comparison of the theory with available experimental data is included, and a program for evaluating effective charge distributions on polyelectrolytes is proposed based upon comparison of experiments with extensions of the theory to higher concentrations.
    Type of Medium: Electronic Resource
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