Compression of polymer brushes: quantitative comparison of self-consistent field theory with experiment

The self-consistent field theory (SCFT) prediction for the compression force between two semi-dilute polymer brushes is compared to the benchmark experiments of Taunton et al. [Nature, 1988, 332, 712]. The comparison is done with previously established parameters, and without any fitting parameters whatsoever. The SCFT provides a significant quantitative improvement over the classical strong-stretching theory (SST), yielding excellent quantitative agreement with the experiment. Contrary to earlier suggestions, chain fluctuations cannot be ignored for normal experimental conditions. Although the analytical expressions of SST provide invaluable aids to understanding the qualitative behavior of polymeric brushes, the numerical SCFT is necessary in order to provide quantitatively accurate predictions.

Strong-segregation limit of the self-consistent field theory for diblock copolymer melts

The self-consistent field theory (SCFT) introduced by Helfand for diblock copolymer melts is expected to converge to the strong-segregation theory (SST) of Semenov in the asymptotic limit, $\chi N \rightarrow \infty$. However, past extrapolations of the lamellar/cylinder and cylinder/sphere phase boundaries, within the standard unit-cell approximation, have cast some doubts on whether or not this is actually true. Here we push the comparison further by extending the SCFT calculations to $\chi N = 512,000$, by accounting for exclusion zones in the coronae of the cylindrical and spherical unit cells, and by examining finite-segregation corrections to SST. In doing so, we provide the first compelling evidence that SCFT does indeed reduce to SST.

Self-consistent field theory for diblock copolymers grafted to a sphere

An efficient numerical self-consistent field theory (SCFT) algorithm is developed for treating structured polymers on spherical surfaces. The method solves the diffusion equations of SCFT with a pseudospectral approach that combines a spherical-harmonics expansion for the angular coordinates with a modified real-space Crank–Nicolson method for the radial direction. The self-consistent field equations are solved with Anderson-mixing iterations using dynamical parameters and an alignment procedure to prevent angular drift of the solution. A demonstration of the algorithm is provided for thin films of diblock copolymer grafted to the surface of a spherical core, in which the sequence of equilibrium morphologies is predicted as a function of diblock composition. The study reveals an array of interesting behaviors as the block copolymer pattern is forced to adapt to the finite surface area of the sphere.

Inverse problems in neural field theory

We study inverse problems in neural field theory, i.e., the construction of synaptic weight kernels yielding a prescribed neural field dynamics. We address the issues of existence, uniqueness, and stability of solutions to the inverse problem for the Amari neural field equation as a special case, and prove that these problems are generally ill-posed. In order to construct solutions to the inverse problem, we first recast the Amari equation into a linear perceptron equation in an infinite-dimensional Banach or Hilbert space. In a second step, we construct sets of biorthogonal function systems allowing the approximation of synaptic weight kernels by a generalized Hebbian learning rule. Numerically, this construction is implemented by the Moore–Penrose pseudoinverse method. We demonstrate the instability of these solutions and use the Tikhonov regularization method for stabilization and to prevent numerical overfitting. We illustrate the stable construction of kernels by means of three instructive examples.

Electrorhythmogenesis and anaesthesia in a physiological mean field theory

We solve eight partial-differential, two-dimensional, nonlinear mean field equations, which describe the dynamics of large populations of cortical neurons. Linearized versions of these equations have been used to generate the strong resonances observed in the human EEG, in particular the α-rhythm (8–), with physiologically plausible parameters. We extend these results here by numerically solving the full equations on a cortex of realistic size, which receives appropriately “colored” noise as extra-cortical input. A brief summary of the numerical methods is provided. As an outlook to future applications, we explain how the effects of GABA-enhancing general anaesthetics can be simulated and present first results.

Understanding the effects of anesthetic agents on the EEG through neural field theory

Anesthetic and analgesic agents act through a diverse range of pharmacological mechanisms. Existing empirical data clearly shows that such "microscopic" pharmacological diversity is reflected in their "macroscopic" effects on the human electroencephalogram (EEG). Based on a detailed mesoscopic neural field model we theoretically posit that anesthetic induced EEG activity is due to selective parametric changes in synaptic efficacy and dynamics. Specifically, on the basis of physiologically constrained modeling, it is speculated that the selective modification of inhibitory or excitatory synaptic activity may differentially effect the EEG spectrum. Such results emphasize the importance of neural field theories of brain electrical activity for elucidating the principles whereby pharmacological agents effect the EEG. Such insights will contribute to improved methods for monitoring depth of anesthesia using the EEG.

Neural population models and cortical field theory: overview

The term neural population models (NPMs) is used here as catchall for a wide range of approaches that have been variously called neural mass models, mean field models, neural field models, bulk models, and so forth. All NPMs attempt to describe the collective action of neural assemblies directly. Some NPMs treat the densely populated tissue of cortex as an excitable medium, leading to spatially continuous cortical field theories (CFTs). An indirect approach would start by modelling individual cells and then would explain the collective action of a group of cells by coupling many individual models together. In contrast, NPMs employ collective state variables, typically defined as averages over the group of cells, in order to describe the population activity directly in a single model. The strength and the weakness of his approach are hence one and the same: simplification by bulk. Is this justified and indeed useful, or does it lead to oversimplification which fails to capture the pheno ...

Finite-stretching corrections to the Milner-Witten-Cates theory for polymer brushes

This paper investigates finite-stretching corrections to the classical Milner-Witten-Cates theory for semi-dilute polymer brushes in a good solvent. The dominant correction to the free energy originates from an entropic repulsion caused by the impenetrability of the grafting surface, which produces a depletion of segments extending a distance $\mu \propto L^{-1}$ from the substrate, where $L$ is the classical brush height. The next most important correction is associated with the translational entropy of the chain ends, which creates the well-known tail where a small population of chains extend beyond the classical brush height by a distance $\xi \propto L^{-1/3}$. The validity of these corrections is confirmed by quantitative comparison with numerical self-consistent field theory.

Converting the nanodomains of a diblock-copolymer thin film from spheres to cylinders with an external electric field

We investigate the ability of an applied electric field to convert the morphology of a diblock-copolymer thin film from a monolayer of spherical domains embedded in the matrix to cylindrical domains that penetrate through the matrix. As expected, the applied field increases the relative stability of cylindrical domains, while simultaneously reducing the energy barrier that impedes the transition to cylinders. The effectiveness of the field is enhanced by a large dielectric contrast between the two block-copolymer components, particularly when the low-dielectric contrast component forms the matrix. Furthermore, the energy barrier is minimized by selecting sphere-forming diblock copolymers that are as compositionally symmetric as possible. Our calculations, which are the most quantitatively reliable to date, are performed using a numerically precise spectral algorithm based on self-consistent-field theory supplemented with an exact treatment for linear dielectric materials.

Electric field alignment in thin films of cylinder-forming diblock copolymer

We investigate thin films of cylinder-forming diblock copolymer confined between electrically charged parallel plates, using self-consistent-field theory ( SCFT) combined with an exact treatment for linear dielectric materials. Our study focuses on the competition between the surface interactions, which tend to orient cylinder domains parallel to the plates, and the electric field, which favors a perpendicular orientation. The effect of the electric field on the relative stability of the competing morphologies is demonstrated with equilibrium phase diagrams, calculated with the aid of a weak-field approximation. As hoped, modest electric fields are shown to have a significant stabilizing effect on perpendicular cylinders, particularly for thicker films. Our improved SCFT-based treatment removes most of the approximations implemented by previous approaches, thereby managing to resolve outstanding qualitative inconsistencies among different approximation schemes.

Undulation instability in block-copolymer lamellae subjected to a perpendicular electric field

We examine the stability of lamellar stacks in the presence of an electric field, E-0, applied normal to the lamellae. Calculations are performed with self-consistent field theory (SCFT) supplemented by an exact treatment of the electrostatic energy for linear dielectric materials. The calculations identify a critical electric field, E-0*, beyond which the lamellar stack becomes unstable with respect to undulations. This E-0* rapidly decreases towards zero as the number of lamellae in the stack diverges. Our quantitative predictions for E-0* are consistent with previous experimental measurements by Xu and co-workers.

Assessment of the RE(OH)3 Ising magnetic materials as possible candidates for the study of transverse-field-induced quantum phase transitions

The LiHoxY1−xF4 Ising magnetic material subject to a magnetic field perpendicular to the Ho3+ Ising direction has shown over the past 20 years to be a host of very interesting thermodynamic and magnetic phenomena. Unfortunately, the availability of other magnetic materials other than LiHoxY1−xF4 that may be described by a transverse-field Ising model remains very much limited. It is in this context that we use here a mean-field theory to investigate the suitability of the Ho(OH)3, Dy(OH)3, and Tb(OH)3 insulating hexagonal dipolar Ising-type ferromagnets for the study of the quantum phase transition induced by a magnetic field, Bx, applied perpendicular to the Ising spin direction. Experimentally, the zero-field critical (Curie) temperatures are known to be Tc≈2.54, 3.48, and 3.72 K, for Ho(OH)3, Dy(OH)3, and Tb(OH)3, respectively. From our calculations we estimate the critical transverse field, Bxc, to destroy ferromagnetic order at zero temperature to be Bxc=4.35, 5.03, and 54.81 T for Ho(OH)3, Dy(OH)3, and Tb(OH)3, respectively. We find that Ho(OH)3, similarly to LiHoF4, can be quantitatively described by an effective S=1/2 transverse-field Ising model. This is not the case for Dy(OH)3 due to the strong admixing between the ground doublet and first excited doublet induced by the dipolar interactions. Furthermore, we find that the paramagnetic (PM) to ferromagnetic (FM) transition in Dy(OH)3 becomes first order for strong Bx and low temperatures. Hence, the PM to FM zero-temperature transition in Dy(OH)3 may be first order and not quantum critical. We investigate the effect of competing antiferromagnetic nearest-neighbor exchange and applied magnetic field, Bz, along the Ising spin direction ẑ on the first-order transition in Dy(OH)3. We conclude from these preliminary calculations that Ho(OH)3 and Dy(OH)3 and their Y3+ diamagnetically diluted variants, HoxY1−x(OH)3 and DyxY1−x(OH)3, are potentially interesting systems to study transverse-field-induced quantum fluctuations effects in hard axis (Ising-type) magnetic materials.