Julia A. Martemyanova

Dense orientationally ordered states of a single semiflexible macromolecule: An expanded ensemble Monte Carlo simulation

Using a coarse-grained model we perform a Monte Carlo simulation of the state behavior of an individual semiflexible macromolecule. Chains consisting of N = 256 and 512 monomer units have been investigated. A recently proposed enhanced sampling Monte Carlo technique for the bond fluctuation model in an expanded ensemble in four-dimensional coordinate space was applied. The algorithm allows one to accelerate the sampling of statistically independent three-dimensional conformations in a dense globular state. We found that the temperature of the intraglobular liquid-solid transition decreases with increasing chain stiffness. We have investigated the possible intraglobular orientationally ordered (i.e., liquid-crystalline) structures and obtained a diagram of states for chains consisting of N = 256 monomer units. This diagram contains regions of stability of coil, two spherical globules (liquid and solid), and rod-like globule conformations. Transitions between the globular states are rounded first-order ones since the states of liquid, solid, and cylinder-like globules do have different internal symmetry.

Computer simulation of stiff-chain polymers

A review of studies on the computer simulation of the phase behavior of various stiff-chain polymer systems is presented. Methods for calculating phase diagrams of a polymer solution in a computer experiment are discussed, including the methods of extended ensembles, entropic simulation, and the Wang-Landau algorithm to obtain the density-of-states function. The authors’ original results on studying the intramolecular orientational and spatial ordering of monomer units in a single stiff-chain macromolecule in the bulk and near a planar adsorbing surface by means of the Wang-Landau algorithm and using the bond-fluctuation lattice model are presented. Corresponding state diagrams are presented for these two cases. For systems of multiple chains, the phenomenon of nematic liquid-crystalline ordering in semi-dilute solutions in the bulk and in a planar layer is considered, and the phase diagrams for these cases are presented. A survey of the published data on some other promising directions of investigation of stiff-chain polymer systems is presented.

Diagram of states and morphologies of flexible-semiflexible copolymer chains: A Monte Carlo simulation

A single copolymer chain consisting of multiple flexible (F) and semiflexible (S) blocks has been studied using a continuum bead-spring model by Stochastic Approximation Monte Carlo simulations, which determine the density of states of the model. The only difference between F and S blocks is the intramolecular bending potential, all non-bonded interactions are equal. The state diagrams for this class of models display multiple nematic phases in the collapsed state, characterized through a demixing of the blocks of different stiffness and orientational ordering of the stiff blocks. We observe dumbbell-like morphologies, lamellar phases, and for the larger block lengths also Saturn-like structures with a core of flexible segments and the stiff segments forming a ring around the core.

Stochastic approximation Monte Carlo algorithm for calculation of diagram of states of a single flexible-semiflexible copolymer chain

We report in this paper on details and special aspects of using the stochastic approximation Monte Carlo (SAMC) algorithm for the calculation of the diagram of states of a single flexible-semiflexible copolymer chain. The SAMC algorithm is a quite recently suggested mathematical generalization of Wang-Landautype algorithms for very precise Monte Carlo estimates of the density of states function g(E) in computer simulations. It has been mathematically proven that the SAMC algorithm converges to the true g(E) function in the limit of infinite sampling, i.e. systematic errors are smaller than statistical errors. However, in practice one faces the reality that statistical errors become small enough only in the limit of the prohibitively large computation time, if one applies this algorithm in a straightforward way, as it is described. Therefore, one usually needs to apply additional technical tricks to accelerate the convergence to a reasonably good function g(E) sampling all most important conformations. In this paper we discuss all details of these inner workings to make the reader aware of real computational efforts, available accuracy, reachable limits, etc. We do this for the first realization of this algorithm for calculation of the two-dimensional density of states function g(E contact, E stiffness) which depends on two contributions to the total energy—intermonomer contact energy and the intramolecular stiffness energy due to chain bending.

Intramolecular structures in a single copolymer chain consisting of flexible and semiflexible blocks: Monte Carlo simulation of a lattice model

We study conformational properties of a single multiblock copolymer chain consisting of flexible and semiflexible blocks. Monomer units of different blocks are equivalent in the sense of the volume interaction potential, but the intramolecular bending potential between successive bonds along the chain is different. We consider a single flexible-semiflexible regular multiblock copolymer chain with equal content of flexible and semiflexible units and vary the length of the blocks and the stiffness parameter. We perform flat histogram type Monte Carlo simulations based on the Wang-Landau approach and employ the bond fluctuation lattice model. We present here our data on different non-trivial globular morphologies which we have obtained in our model for different values of the block length and the stiffness parameter. We demonstrate that the collapse can occur in one or in two stages depending on the values of both these parameters and discuss the role of the inhomogeneity of intraglobular distributions of monomer units of both flexible and semiflexible blocks. For short block length and/or large stiffness the collapse occurs in two stages, because it goes through intermediate (meta-)stable structures, like a dumbbell shaped conformation. In such conformations the semiflexible blocks form a cylinder-like core, and the flexible blocks form two domains at both ends of such a cylinder. For long block length and/or small stiffness the collapse occurs in one stage, and in typical conformations the flexible blocks form a spherical core of a globule while the semiflexible blocks are located on the surface and wrap around this core.