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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 99 (1995), S. 1505-1515 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , 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 111 (1999), S. 5232-5240 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: I use a Landau theory to study the behavior of A–B heteropolymers with disordered sequences immersed in a binary solvent mixture. Segments of type A are preferentially solvated in one type of solvent, and those of type B prefer the other type of solvent. At high temperatures, the behavior is qualitatively the same as that in a single solvent. As the temperature approaches the critical temperature for solvent demixing, however, the chain conformational statistics change dramatically. A phase transition occurs driven by the long-range solvent density fluctuations. The transition is one where on scales larger than a preferred length the chain is collapsed and microphase ordered. On shorter scales it is disordered and exhibits self-avoiding walk statistics. In many circumstances this domain size acquires a limiting value and the system cannot order on shorter length scales by reducing temperature. The ordering disappears when the critical point is approached too closely. Predictions are made for scattering profiles that may be observed in neutron-scattering experiments. © 1999 American Institute of Physics.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 1683-1687 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Random heteropolymers (RHPs) with uncorrelated sequence fluctuations on the segmental scale can undergo a transition wherein, below a certain temperature, the thermodynamics is determined by a few dominant conformations. We study this "freezing" transition for RHPs with correlated sequence fluctuations. Specifically, we apply our theory to the case where the correlations decay with a single correlation length; a pragmatically realizable example is provided by random block copolymers. Our results show that the temperature at which freezing occurs grows with the block length of such polymers. Freezing also occurs on the scale of the correlation length, thus making experimental observation of this phenomenon (a consequence of frustration coupled with quenched disorder) more accessible. The results are rationalized on physical grounds. © 1998 American Institute of Physics.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 108 (1998), S. 1676-1682 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the adsorption of random heteropolymers (RHPs) on disordered multifunctional surfaces. Recent replica calculations suggest that when the statistics describing the sequence distribution and the surface site distributions are related in a special way, a first-order adsorption transition occurs in such systems. This phenomenon of recognition between RHPs and disordered surfaces due to statistical pattern matching is studied via Monte Carlo simulations and a simple nonreplica theory. The theory serves to elucidate the simulation results, and suggests that the origin of the first-order adsorption transition is the suppression of loop fluctuations due to competing interactions and the quenched disorder (i.e., frustration). © 1998 American Institute of Physics.
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  • 5
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We derive a Landau free energy functional for polymeric mixtures containing components with different sequence statistics. We then apply this general field theory to two mixtures that belong to the Ising universality class: mixtures of two different linear random copolymers, and ternary systems of linear random copolymers and two homopolymers. We discuss the instability conditions for the homogeneous state of these mixtures, and calculate the structure factors for different components in the homogeneous state. The structure factors show interesting features which can directly be compared with scattering experiments carried out with selectively deuterated samples. We also work out the eigenmodes representing the least stable concentration fluctuations for these mixtures. The nature of these concentration fluctuations provides information regarding the ordered phases and the kinetic pathways that lead to them. We find various demixing modes for different characteristics of the two mixtures (e.g., average compositions, statistical correlation lengths, and volume fractions). © 2000 American Institute of Physics.
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 112 (2000), S. 1598-1605 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We use a Landau theory to study the instability of the homogeneous state of a mixture of linear random copolymers and diblock copolymers. Interesting features of the calculated structure factors for different components of the mixture are found, which can be directly compared with scattering experiments with selectively deuterated samples. We also investigate the least stable concentration fluctuations and find four different types of segregation modes at the spinodal depending upon the characteristics of the mixture (e.g., average compositions, statistical correlation lengths and volume fractions). The different segregation modes are also indicative of the kinetic pathways leading to the formation of ordered microstructures. Experiments probing these pathways are suggested. © 2000 American Institute of Physics.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 104 (1996), S. 7306-7312 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We develop a model for the adsorption of random heteropolymers onto solid surfaces from solutions that have a finite concentration of polymer. Previous studies that properly average over the quenched sequence distribution have been concerned with isolated chains near surfaces. Our self-consistent-field theory predicts a transition from situations where the surface segment density is enhanced compared with bulk solution concentration to one wherein the surface segment density is depleted. For a specific chemical identity of the random heteropolymer segments and the surface, this adsorption–depletion transition occurs above a threshold value of the strength of the sequence fluctuations. This intriguing finding can be tested directly via neutron scattering experiments (in the reflection mode), and offers opportunities for manipulating interfacial properties. The variation of the excess surface density of segments with polymer concentration in solution near the adsorption–depletion transition is also elucidated. © 1996 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 100 (1994), S. 1528-1541 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider the diffusion of ionic species in technologically relevant materials such as zeolites. These materials are characterized by a disordered density distribution of charged sites that couple with the diffusing species. We present a model for ion diffusion in a specific form of charged disorder. This is a primitive model for ion diffusion in charged or acidic zeolites. The theory relies on a path integral representation of the propagator, and a Gaussian field theory for the effects of the disorder. We use the Feynman–Bogoliubov variational method to treat the model, and calculate the diffusion coefficient for ions in a medium characterized by randomly located charges. Numerical solution of our equations, and asymptotic analyses of the same, show that in our theory there is a crossover from diffusive to subdiffusive behavior beyond a threshold value for the average density of the disorder. This threshold coincides with the actual diffusion changing from processes well approximated by Gaussian paths to those involving escapes from deep potential wells and barrier crossings. These results are discussed in the context of recent field-theoretic and renormalization group approaches to the problem of diffusion in random media. Our approach to diffusion in random media appears reasonably general and should be applicable to many technologically relevant problems, and is not compute intensive.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 105 (1996), S. 7842-7856 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In many applications, it is desirable to control interfacial properties by employing adsorbed polymer layers. In this work, we study the adsorption of random heteropolymers and find a rich surface phase diagram that suggest ways in which the properties of the adsorbed layers can be controlled rather precisely by manipulating the physical conditions. Specifically, we present a comprehensive field-theoretic analysis of the surface phase diagram of a solution of random heteropolymers interacting with a chemically homogeneous solid surface, and find many surface transitions that may be exploited in applications. The different types of polymer segments interact with the solid surface in arbitrarily different ways. Our analysis, wherein a replica method is employed to average over the quenched sequence fluctuations, allows us to obtain the surface free energy functionals that show that our problem partially resembles a semi-infinite Ising spin system. Thus, akin to the Ising system, the phase diagram exhibits exotic surface transitions. In the infinitely dilute limit we find four "massless'' transition lines: the ordinary (OT), the surface (ST), the extraordinary (ET), and the special (SPT) transition. At finite bulk solution concentration, we find two transitions; viz. the OT and the adsorption–depletion (ADT) transitions. The nature of the critical points that reside on the transition lines are analyzed, and the physical meaning of each of the surface transitions is elucidated. Our results are related to experiments and it is shown that the interesting behavior that random heteropolymers exhibit near surfaces is due to the quenched sequence fluctuations. © 1996 American Institute of Physics.
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  • 10
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 24 (1991), S. 5226-5229 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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