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At least 289 records · Page 16

Theoretical Basis for Finite Difference Extrapolation of Sonic Boom Signatures

Calculation of sonic boom signatures for aircraft has traditionally followed the methods of Whitham' and Walkden. The wave disturbance generated by the vehicle is obtained by area rule linearized supersonic flow methods, which yield a locally axisymmetric asymptotic solution. This solution is acoustic in nature, i.e., first order in disturbance quantities, and corresponds to ray acoustics. Cumulative nonlinear distortion of the signature is incorporated by using this solution to adjust propagation speed to first order, thus yielding a solution second order in disturbance quantities. The effects of atmospheric gradients are treated by Blokhintzov's method of geometrical acoustics. Both nonlinear signature evolution and ray tracing are applied as if the pressure field very close to the vehicle were actually that given by the source term (the 'F-function') of the asymptotic linearized flow solution. The viewpoint is thus that the flow solution exists at a small radius near the vehicle, and may be treated as an input to an extrapolation procedure consisting of ray tracing and nonlinear aging. The F-function is often regarded as a representation of a near-field pressure signature, and it is common for computational implementations to treat it interchangeably with the pressure signature. There is a 'matching radius' between the source function and the subsequent propagation extrapolation. This viewpoint has been supported by wind tunnel tests of simple models, and very typically yields correct results for actual flight vehicles. The assumption that the F-function and near-field signature are interchangeable is generally not correct. The flowfield of a vehicle which is not axisymmetric contains crossflow components which are very significant at small radii and less so at larger distances. From an acoustical viewpoint, the crossflow is equivalent to source diffraction portions of the wave field. Use of the F-function as a near field signature effectively assumes that the diminution of the crossflow/diffraction component may be applied all at once at the matching radius noted above. This approximation, though not rigorously validated, is responsible for the usual correct far-field results. On the other hand, if an actual near-field signature (either from wind tunnel or CFD data) is used at a starting point rather than one based on th effective source distribution, the predicted far-field signature is generally wrong.

Plotkin, Kenneth J.↗

High-Fidelity Generalization Method of Cells for Inelastic Periodic Multiphase Materials

An extension of a recently-developed linear thermoelastic theory for multiphase periodic materials is presented which admits inelastic behavior of the constituent phases. The extended theory is capable of accurately estimating both the effective inelastic response of a periodic multiphase composite and the local stress and strain fields in the individual phases. The model is presently limited to materials characterized by constituent phases that are continuous in one direction, but arbitrarily distributed within the repeating unit cell which characterizes the material's periodic microstructure. The model's analytical framework is based on the homogenization technique for periodic media, but the method of solution for the local displacement and stress fields borrows concepts previously employed by the authors in constructing the higher-order theory for functionally graded materials, in contrast with the standard finite-element solution method typically used in conjunction with the homogenization technique. The present approach produces a closed-form macroscopic constitutive equation for a periodic multiphase material valid for both uniaxial and multiaxial loading. The model's predictive accuracy in generating both the effective inelastic stress-strain response and the local stress said inelastic strain fields is demonstrated by comparison with the results of an analytical inelastic solution for the axisymmetric and axial shear response of a unidirectional composite based on the concentric cylinder model, and with finite-element results for transverse loading.

Aboudi, Jacob↗

Quantum time dynamics employing the Yang-Baxter equation for circuit compression

Quantum time dynamics (QTD) is considered a promising problem for quantum supremacy on near-term quantum computers. However, QTD quantum circuits grow with increasing time simulations. This study focuses on simulating the time dynamics of one-dimensional (1D) integrable spin chains with nearest-neighbor interactions. We have proved the existence of a reflection symmetry in the quantum circuit employed for simulating the time evolution of certain classes of 1D Heisenberg model Hamiltonians by virtue of the quantum Yang-Baxter equation, and how this symmetry can be exploited to compress and produce a shallow quantum circuit. With this compression scheme, the depth of the quantum circuit becomes independent of step size and only depends on the number of spins. We show that the depth of the compressed circuit is rigorously a linear function of the system size for the studied Heisenberg model Hamiltonians in the present work. As a consequence, the number of CNOT gates in the compressed circuit only scales quadratically with the system size, which allows for the simulations of time dynamics of very large 1D spin chains. We derive the compressed circuit representations for different special cases of the Heisenberg Hamiltonian. We compare and demonstrate the effectiveness of this approach by performing simulations on quantum computers.

1-dimensional spin chains↗

NASA Tech Briefs, September 2012

Topics covered include: Beat-to-Beat Blood Pressure Monitor; Measurement Techniques for Clock Jitter; Lightweight, Miniature Inertial Measurement System; Optical Density Analysis of X-Rays Utilizing Calibration Tooling to Estimate Thickness of Parts; Fuel Cell/Electrochemical Cell Voltage Monitor; Anomaly Detection Techniques with Real Test Data from a Spinning Turbine Engine-Like Rotor; Measuring Air Leaks into the Vacuum Space of Large Liquid Hydrogen Tanks; Antenna Calibration and Measurement Equipment; Glass Solder Approach for Robust, Low-Loss, Fiber-to-Waveguide Coupling; Lightweight Metal Matrix Composite Segmented for Manufacturing High-Precision Mirrors; Plasma Treatment to Remove Carbon from Indium UV Filters; Telerobotics Workstation (TRWS) for Deep Space Habitats; Single-Pole Double-Throw MMIC Switches for a Microwave Radiometer; On Shaft Data Acquisition System (OSDAS); ASIC Readout Circuit Architecture for Large Geiger Photodiode Arrays; Flexible Architecture for FPGAs in Embedded Systems; Polyurea-Based Aerogel Monoliths and Composites; Resin-Impregnated Carbon Ablator: A New Ablative Material for Hyperbolic Entry Speeds; Self-Cleaning Particulate Prefilter Media; Modular, Rapid Propellant Loading System/Cryogenic Testbed; Compact, Low-Force, Low-Noise Linear Actuator; Loop Heat Pipe with Thermal Control Valve as a Variable Thermal Link; Process for Measuring Over-Center Distances; Hands-Free Transcranial Color Doppler Probe; Improving Balance Function Using Low Levels of Electrical Stimulation of the Balance Organs; Developing Physiologic Models for Emergency Medical Procedures Under Microgravity; PMA-Linked Fluorescence for Rapid Detection of Viable Bacterial Endospores; Portable Intravenous Fluid Production Device for Ground Use; Adaptation of a Filter Assembly to Assess Microbial Bioburden of Pressurant Within a Propulsion System; Multiplexed Force and Deflection Sensing Shell Membranes for Robotic Manipulators; Whispering Gallery Mode Optomechanical Resonator; Vision-Aided Autonomous Landing and Ingress of Micro Aerial Vehicles; Self-Sealing Wet Chemistry Cell for Field Analysis; General MACOS Interface for Modeling and Analysis for Controlled Optical Systems; Mars Technology Rover with Arm-Mounted Percussive Coring Tool, Microimager, and Sample-Handling Encapsulation Containerization Subsystem; Fault-Tolerant, Real-Time, Multi-Core Computer System; Water Detection Based on Object Reflections; SATPLOT for Analysis of SECCHI Heliospheric Imager Data; Plug-in Plan Tool v3.0.3.1; Frequency Correction for MIRO Chirp Transformation Spectroscopy Spectrum; Nonlinear Estimation Approach to Real-Time Georegistration from Aerial Images; Optimal Force Control of Vibro-Impact Systems for Autonomous Drilling Applications; Low-Cost Telemetry System for Small/Micro Satellites; Operator Interface and Control Software for the Reconfigurable Surface System Tri-ATHLETE; and Algorithms for Determining Physical Responses of Structures Under Load.

Source record↗

A new and alternative look at nonlinear Alfvénic states

The formulation for studying nonlinear Alfvenic states, sustainable in Hall Magnetohydrodynamics (HMHD), becomes considerably simpler and more tractable when circularly polarized Beltrami vectors (the eigenstates of linear HMHD) are used as the basis functions. Nonlinear HMHD is, then, reduced to a rather simple looking set of scalar equations from which a model problem of three interacting Beltrami modes is formulated and analytically solved. The triplet interactions span a variety of familiar nonlinear processes leading to a redistribution as well as periodic exchange of energy. The energy exchange processes (whose strength is measured by an energy exchange/depletion time) will, perhaps, play a dominant role in determining the spectral content of an eventual Alfvenic state. All nonlinearities (sensitive functions of the interacting wave vectors) operate at par, and none is dominant over any substantial region of k-space; their intricate interplay prevents a “universal” picture from emerging; few generalizations on the processes that may, for instance, lead to a turbulent state, are possible. However, the theory can definitely claim: (1) the energy tends to flow from lower to higher k and (2) the higher k z (in the direction of the ambient magnetic field) components of a mode with a given k are depleted/oscillate faster—in some cases much faster. It is noteworthy that the mode coupling is the strongest (with the shortest depletion time) when the participating wave vectors are nearly perpendicular; perhaps, an expected consequence of the curl (cross product) nonlinearities. Numerical simulations will be necessary to help create a fully reliable picture.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Bouger's Law Shell Ionospheric Transfer Function

Ionospheric transfer function (ITF) algorithms determine the effects of the ionosphere on an electromagnetic (EM) radio-frequency (RF) signal as it propagates through. In this report, the Bouger’s law shell model is outlined. This ITF is very similar to the Snell’s Law Shell ITF; however, in this formulation, plasma parameters in the ionosphere are allowed to change radially. This algorithm is expressed in the frequency domain. In this way, it is applied as linear time invariant (LTI) filter function. Signals in this report are assumed to have only a single component (i.e. x, y or z in a rectangular coordinate system). Multi-component signals can be treated simply by applying the specific ITF to each component separately.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Permutation-adapted complete and independent basis for atomic cluster expansion descriptors

Atomic cluster expansion (ACE) methods provide a systematic way to describe particle local environments of arbitrary body order. For practical applications it is often required that the basis of cluster functions be symmetrized with respect to rotations and permutations. Existing methodologies yield sets of symmetrized functions that are over-complete. These methodologies thus require an additional numerical procedure, such as singular value decomposition (SVD), to eliminate redundant functions. In this work, it is shown that analytical linear relationships for subsets of cluster functions may be derived using recursion and permutation properties of generalized Wigner symbols. From these relationships, subsets (blocks) of cluster functions can be selected such that, within each block, functions are guaranteed to be linearly independent. It is conjectured that this block-wise independent set of permutation-adapted rotation and permutation invariant (PA-RPI) functions forms a complete, independent basis for ACE. Along with the first analytical proofs of block-wise linear dependence of ACE cluster functions and other theoretical arguments, numerical results are offered to demonstrate this. The utility of the method is demonstrated in the development of an ACE interatomic potential for tantalum. Using the new basis functions in combination with Bayesian compressive sensing sparse regression, some high degree descriptors are observed to persist and help achieve high-accuracy models.

Angular momentum↗

Signatures of cysteine oxidation on muscle structural and contractile proteins are associated with physical performance and muscle function in older adults: Study of Muscle, Mobility and Aging (SOMMA)

Oxidative stress is considered a contributor to declining muscle function and mobility during aging; however, the underlying molecular mechanisms remain poorly described. We hypothesized that greater levels of cysteine (Cys) oxidation on muscle proteins are associated with decreased measures of mobility. Herein, we applied a novel redox proteomics approach to measure reversible protein Cys oxidation in vastus lateralis muscle biopsies collected from 56 subjects in the Study of Muscle, Mobility and Aging (SOMMA), a community-based cohort study of individuals aged 70 years and older. We tested whether levels of Cys oxidation on key muscle proteins involved in muscle structure and contraction were associated with muscle function (leg power and strength), walking speed, and fitness (VO 2 peak on cardiopulmonary exercise testing) using linear regression models adjusted for age, sex, and body weight. Higher oxidation levels of select nebulin Cys sites were associated with lower VO 2 peak, while greater oxidation of myomesin-1, myomesin-2, and nebulin Cys sites was associated with slower walking speed. Higher oxidation of Cys sites in key proteins such as myomesin-2, alpha-actinin-2, and skeletal muscle alpha-actin were associated with lower leg power and strength. We also observed an unexpected correlation (R = 0.48) between a higher oxidation level of eight Cys sites in alpha-actinin-3 and stronger leg power. Despite this observation, the results generally support the hypothesis that Cys oxidation of muscle proteins impairs muscle power and strength, walking speed, and cardiopulmonary fitness with aging.

59 BASIC BIOLOGICAL SCIENCES↗

Three-state harmonic models for photoinduced charge transfer

A widely used strategy for simulating the charge transfer between donor and acceptor electronic states in an all-atom anharmonic condensedphase system is based on invoking linear response theory to describe the system in terms of an effective spin-boson model Hamiltonian. Extending this strategy to photoinduced charge transfer processes requires also taking into consideration the ground electronic state in addition to the excited donor and acceptor electronic states. In this paper, we revisit the problem of describing such nonequilibrium processes in terms of an effective three-state harmonic model. We do so within the framework of nonequilibrium Fermi’s golden rule (NE-FGR) in the context of photoinduced charge transfer in the carotenoid–porphyrin–C 60 (CPC 60 ) molecular triad dissolved in explicit tetrahydrofuran (THF). To this end, we consider different ways for obtaining a three-state harmonic model from the equilibrium autocorrelation functions of the donor–acceptor, donor–ground, and acceptor–ground energy gaps, as obtained from all-atom molecular dynamics simulations of the CPC 60 /THF system. The quantum-mechanically exact time-dependent NE-FGR rate coefficients for two different charge transfer processes in two different triad conformations are then calculated using the effective three-state model Hamiltonians as well as a hierarchy of more approximate expressions that lead to the instantaneous Marcus theory limit. Our results show that the photoinduced charge transfer in CPC 60 /THF can be described accurately by the effective harmonic three-state models and that nuclear quantum effects are small in this system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The evaluation of the OSGLR algorithm for restructurable controls

The detection and isolation of commercial aircraft control surface and actuator failures using the orthogonal series generalized likelihood ratio (OSGLR) test was evaluated. The OSGLR algorithm was chosen as the most promising algorithm based on a preliminary evaluation of three failure detection and isolation (FDI) algorithms (the detection filter, the generalized likelihood ratio test, and the OSGLR test) and a survey of the literature. One difficulty of analytic FDI techniques and the OSGLR algorithm in particular is their sensitivity to modeling errors. Therefore, methods of improving the robustness of the algorithm were examined with the incorporation of age-weighting into the algorithm being the most effective approach, significantly reducing the sensitivity of the algorithm to modeling errors. The steady-state implementation of the algorithm based on a single cruise linear model was evaluated using a nonlinear simulation of a C-130 aircraft. A number of off-nominal no-failure flight conditions including maneuvers, nonzero flap deflections, different turbulence levels and steady winds were tested. Based on the no-failure decision functions produced by off-nominal flight conditions, the failure detection performance at the nominal flight condition was determined. The extension of the algorithm to a wider flight envelope by scheduling the linear models used by the algorithm on dynamic pressure and flap deflection was also considered. Since simply scheduling the linear models over the entire flight envelope is unlikely to be adequate, scheduling of the steady-state implentation of the algorithm was briefly investigated.

Bonnice, W. F.↗

Dynamics of the North Sea pole tide reconsidered

The anomalous tide in the North Sea, driven by the Chandler wobble, is here re-examined. A previously published solution in which these 'pole tide' observations were explained as a forced co-oscillation from the deep water tide is shown to be untenable, because it is very unlikely that the deep ocean tide is anything but equilibrium. Using the same physics as in the previous solution (viscous, linear, quasi-geostrophic dynamics), it is now suggested that the only plausible explanation is that there is a coincidental resonance between the long-wavelength branch topographic Rossby wave of the North Sea and the direct driving by the pole tide potential. This resonance is not a basin-resonance, but that of a free wave driven by a travelling forcing function. Simplified models reproduce the observations in qualitative fashion. If this explanation is the correct one, then the Arctic seas north of Asia and North America appear to be likely candidates as other regions where there may be a large pole tide response and, hence, a locus of wobble dissipation. Given the difficulties of observation, the long times required, and the general instability of the dissipation calculation with the simplified analytical model, probably a numerical model will be required for further progress.

Wunsch, Carl↗

Active stabilization to prevent surge in centrifugal compression systems

This report documents an experimental and analytical study of the active stabilization of surge in a centrifugal engine. The aims of the research were to extend the operating range of a compressor as far as possible and to establish the theoretical framework for the active stabilization of surge from both an aerodynamic stability and a control theoretic perspective. In particular, much attention was paid to understanding the physical limitations of active stabilization and how they are influenced by control system design parameters. Previously developed linear models of actively stabilized compressors were extended to include such nonlinear phenomena as bounded actuation, bandwidth limits, and robustness criteria. This model was then used to systematically quantify the influence of sensor-actuator selection on system performance. Five different actuation schemes were considered along with four different sensors. Sensor-actuator choice was shown to have a profound effect on the performance of the stabilized compressor. The optimum choice was not unique, but rather shown to be a strong function of some of the non-dimensional parameters which characterize the compression system dynamics. Specifically, the utility of the concepts were shown to depend on the system compliance to inertia ratio ('B' parameter) and the local slope of the compressor speedline. In general, the most effective arrangements are ones in which the actuator is most closely coupled to the compressor, such as a close-coupled bleed valve inlet jet, rather than elsewhere in the flow train, such as a fuel flow modulator. The analytical model was used to explore the influence of control system bandwidth on control effectiveness. The relevant reference frequency was shown to be the compression system's Helmholtz frequency rather than the surge frequency. The analysis shows that control bandwidths of three to ten times the Helmholtz frequency are required for larger increases in the compressor flow range. This has important implications for implementation in gas turbine engines since the Helmholtz frequencies can be over 100 Hz, making actuator design extremely challenging.

Epstein, Alan H.↗

Bayesian Optimization Framework for Imperfect Data or Models

Conventional Bayesian optimization methods implicitly assume that the data and model being optimized are “perfect.” This assumption leads to inaccurate posterior probability distribution functions (PDFs) when applied to “imperfect” data or models. The new Bayesian optimization framework presented in this report provides a way to parameterize the effect of imperfections usually encountered in a prior PDF of generalized data or a model on the posterior PDF. The effects of imperfections are parameterized by a set of constraints imposed on the posterior expectation values of deviations between the data and the model and on their covariance matrix elements. A particular set of values for these constraints conveys an evaluator’s best estimate of the effect of imperfections on the corresponding posterior expectation values. When a prior PDF of generalized data is assumed to be normal, an expression for a posterior PDF satisfying an arbitrary set of constraints is derived analytically for linear models. An analogous iterative algorithm is given for nonlinear models. The corresponding posterior PDF should be used to estimate any posterior expectation values in the presence of imperfections parameterized by that set of constraints. A posterior PDF of a conventional Bayesian optimization method is recovered analytically when all evaluator-specified constraints are set to zero (i.e., in the absence of any imperfections). The analytical expressions derived in this report for normal PDFs and linear models were verified numerically by a Metropolis–Hastings Monte Carlo method. The methods presented herein could be applied to any kind of data or models, including differential cross-section data or integral benchmark experiments.

97 MATHEMATICS AND COMPUTING↗

Interseasonal Variations in the Middle Atmosphere Forced by Gravity Waves

In our Numerical Spectral Model (NSM), which incorporates Hines' Doppler Spread Parameterization, gravity waves (GW) propagating in the east/west direction can generate the essential features of the observed equatorial oscillations in the zonal circulation and in particular the QBO (quasi-biennial oscillation) extending from the stratosphere into the upper mesosphere. We report here that the NSM also produces inter-seasonal variations in the zonally symmetric (m = 0) meridional circulation. A distinct but variable meridional wind oscillation (MWO) is generated, which appears to be the counterpart to the QBO. With a vertical grid-point resolution of about 0.5 km, the NSM produces the MWO through momentum deposition of GWs propagating in the north/south direction. The resulting momentum source represents a third (generally odd) order non-linear function of the meridional winds, and this enables the oscillation, as in the case of the QBO for the zonal winds. Since the meridional winds are relatively small compared to the zonal winds, however, the vertical wavelength that maintains the MWO is much smaller, i.e., only about 10 km instead of 40 km for the QBO. Consistent with the associated increase of the viscous stress, the period of the MWO is then short compared with that of the QBO, i.e., only about two to four months. Depending on the strength of the GW forcing, the computed amplitudes of the MWO are typically 4 m/s in the upper stratosphere and mesosphere, and the associated temperature amplitudes are between about 2 and 3 K. These amplitudes may be observable with the instruments on the TIMED spacecraft. Extended computer simulations with the NSM in 2D (two-dimensional) and 3D (three-dimensional) reveal that the MWO is modulated by and in turn influences the QBO.

Mayr, H. G.↗

Variability Selected Low-Luminosity Active Galactic Nuclei in the 4 Ms Chandra Deep Field-South

The 4 Ms Chandra Deep Field-South (CDF-S) and other deep X-ray surveys have been highly effective at selecting active galactic nuclei (AGN). However, cosmologically distant low-luminosity AGN (LLAGN) have remained a challenge to identify due to significant contribution from the host galaxy. We identify long-term X ray variability (approx. month years, observed frame) in 20 of 92 CDF-S galaxies spanning redshifts approx equals 00.8 - 1.02 that do not meet other AGN selection criteria. We show that the observed variability cannot be explained by X-ray binary populations or ultraluminous X-ray sources, so the variability is most likely caused by accretion onto a supermassive black hole. The variable galaxies are not heavily obscured in general, with a stacked effective power-law photon index of Gamma(sub Stack) approx equals 1.93 +/- 0.13, and arc therefore likely LLAGN. The LLAGN tend to lie it factor of approx equal 6-89 below the extrapolated linear variability-luminosity relation measured for luminous AGN. This may he explained by their lower accretion rates. Variability-independent black-hole mass and accretion-rate estimates for variable galaxies show that they sample a significantly different black hole mass-accretion-rate space, with masses a factor of 2.4 lower and accretion rates a factor of 22.5 lower than variable luminous AGNs at the same redshift. We find that an empirical model based on a universal broken power-law power spectral density function, where the break frequency depends on SMBH mass and accretion rate, roughly reproduces the shape, but not the normalization, of the variability-luminosity trends measured for variable galaxies and more luminous AGNs.

Young, M.↗

The Constitutive Modeling of Thin Films with Randon Material Wrinkles

Material wrinkles drastically alter the structural constitutive properties of thin films. Normally linear elastic materials, when wrinkled, become highly nonlinear and initially inelastic. Stiffness' reduced by 99% and negative Poisson's ratios are typically observed. This paper presents an effective continuum constitutive model for the elastic effects of material wrinkles in thin films. The model considers general two-dimensional stress and strain states (simultaneous bi-axial and shear stress/strain) and neglects out of plane bending. The constitutive model is derived from a traditional mechanics analysis of an idealized physical model of random material wrinkles. Model parameters are the directly measurable wrinkle characteristics of amplitude and wavelength. For these reasons, the equations are mechanistic and deterministic. The model is compared with bi-axial tensile test data for wrinkled Kaptong(Registered Trademark) HN and is shown to deterministically predict strain as a function of stress with an average RMS error of 22%. On average, fitting the model to test data yields an RMS error of 1.2%

Murphey, Thomas W.↗

Molecular hydrodynamic theory of the velocity autocorrelation function

The velocity autocorrelation function (VACF) encapsulates extensive information about a fluid’s molecular-structural and hydrodynamic properties. We address the following fundamental question: How well can a purely hydrodynamic description recover the molecular features of a fluid as exhibited by the VACF? To this end, we formulate a bona fide hydrodynamic theory of the tagged-particle VACF for simple fluids. Our approach is distinguished from previous efforts in two key ways: collective hydrodynamic modes and tagged-particle self-motion are modeled by linear hydrodynamic equations; the fluid’s spatial velocity power spectrum is identified as a necessary initial condition for the momentum current correlation. This formulation leads to a natural physical interpretation of the VACF as a superposition of products of quasinormal hydrodynamic modes weighted commensurately with the spatial velocity power spectrum, the latter of which appears to physically bridge continuum hydrodynamical behavior and discrete-particle kinetics. The methodology yields VACF calculations quantitatively on par with existing approaches for liquid noble gases and alkali metals. Furthermore, we obtain a new, hydrodynamic form of the self-intermediate scattering function whose description has been extended to low densities where the Schmidt number is of order unity; various calculations are performed for gaseous and supercritical argon to support the general validity of the theory. Excellent quantitative agreement is obtained with recent MD calculations for a dense supercritical Lennard-Jones fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unified understanding of the impact of semiflexibility, concentration, and molecular weight on macromolecular-scale ring diffusion

Conformationally fluctuating, globally compact macromolecules such as polymeric rings, single-chain nanoparticles, microgels, and many-arm stars display complex dynamic behaviors due to their rich topological structure and intermolecular organization. Synthetic rings are hybrid objects with conformations that display both ideal random walk and compact globular features, which can serve as models of genomic DNA. To date, emphasis has been placed on the effect of ring molecular weight on their unusual behaviors. Here, we combine simulations and a microscopic force-level theory to build a unified understanding for how key aspects of ring dynamics depend on different tunable molecular properties including backbone rigidity, monomer concentration, degree of traditional entanglement, and molecular weight. Our large-scale molecular dynamics simulations of ring melts with very different backbone stiffnesses reveal unanticipated behaviors which agree well with our generalized theory. This includes a universal master curve for center-of-mass diffusion constants as a function of molecular weight scaled by a chemistry and thermodynamic state-dependent critical molecular weight that generalizes the concept of an entanglement cross-over for linear chains. The key physics is how backbone rigidity and monomer concentration induced changes of the entanglement length, interring packing, degree of interpenetration, and liquid compressibility slow down space-time dynamic-force correlations on macromolecular scales. A power law decay of the center-of-mass diffusion constant with inverse molecular weight squared is the first consequence, followed by an ultraslow activated hopping transport regime. Our results set the stage to address slow dynamics and kinetic arrest in different families of compact synthetic and biological polymeric systems.

Science & Technology - Other Topics↗