Coarse Molecular Dynamics of a Peptide Fragment: Free Energy, Kinetics, and Long-Time Dynamics Computations

We present a ``coarse molecular dynamics'' approach and apply it to studying the kinetics and thermodynamics of a peptide fragment dissolved in water. Short bursts of appropriately initialized simulations are used to infer the deterministic and stochastic components of the peptide motion parametrized by an appropriate set of coarse variables. Techniques from traditional numerical analysis (Newton-Raphson, coarse projective integration) are thus enabled; these techniques help analyze important features of the free-energy landscape (coarse transition states, eigenvalues and eigenvectors, transition rates, etc.). Reverse integration of (irreversible) expected coarse variables backward in time can assist escape from free energy minima and trace low-dimensional free energy surfaces. To illustrate the ``coarse molecular dynamics'' approach, we combine multiple short (0.5-ps) replica simulations to map the free energy surface of the ``alanine dipeptide'' in water, and to determine the ~ 1/(1000 ps) rate of interconversion between the two stable configurational basins corresponding to the alpha-helical and extended minima.Comment: The article has been submitted to "The Journal of Chemical Physics.

The fully-implicit log-conformation formulation and its application to three-dimensional flows

The stable and efficient numerical simulation of viscoelastic flows has been a constant struggle due to the High Weissenberg Number Problem. While the stability for macroscopic descriptions could be greatly enhanced by the log-conformation method as proposed by Fattal and Kupferman, the application of the efficient Newton-Raphson algorithm to the full monolithic system of governing equations, consisting of the log-conformation equations and the Navier-Stokes equations, has always posed a problem. In particular, it is the formulation of the constitutive equations by means of the spectral decomposition that hinders the application of further analytical tools. Therefore, up to now, a fully monolithic approach could only be achieved in two dimensions, as, e.g., recently shown in [P. Knechtges, M. Behr, S. Elgeti, Fully-implicit log-conformation formulation of constitutive laws, J. Non-Newtonian Fluid Mech. 214 (2014) 78-87]. The aim of this paper is to find a generalization of the previously made considerations to three dimensions, such that a monolithic Newton-Raphson solver based on the log-conformation formulation can be implemented also in this case. The underlying idea is analogous to the two-dimensional case, to replace the eigenvalue decomposition in the constitutive equation by an analytically more "well-behaved" term and to rely on the eigenvalue decomposition only for the actual computation. Furthermore, in order to demonstrate the practicality of the proposed method, numerical results of the newly derived formulation are presented in the case of the sedimenting sphere and ellipsoid benchmarks for the Oldroyd-B and Giesekus models. It is found that the expected quadratic convergence of Newton's method can be achieved.Comment: 21 pages, 9 figure

Some Further Results for the Stationary Points and Dynamics of Supercooled Liquids

We present some new theoretical and computational results for the stationary points of bulk systems. First we demonstrate how the potential energy surface can be partitioned into catchment basins associated with every stationary point using a combination of Newton-Raphson and eigenvector-following techniques. Numerical results are presented for a 256-atom supercell representation of a binary Lennard-Jones system. We then derive analytical formulae for the number of stationary points as a function of both system size and the Hessian index, using a framework based upon weakly interacting subsystems. This analysis reveals a simple relation between the total number of stationary points, the number of local minima, and the number of transition states connected on average to each minimum. Finally we calculate two measures of localisation for the displacements corresponding to Hessian eigenvectors in samples of stationary points obtained from the Newton-Raphson-based geometry optimisation scheme. Systematic differences are found between the properties of eigenvectors corresponding to positive and negative Hessian eigenvalues, and localised character is most pronounced for stationary points with low values of the Hessian index.Comment: 16 pages, 2 figure

Coarse Stability and Bifurcation Analysis Using Stochastic Simulators: Kinetic Monte Carlo Examples

We implement a computer-assisted approach that, under appropriate conditions, allows the bifurcation analysis of the coarse dynamic behavior of microscopic simulators without requiring the explicit derivation of closed macroscopic equations for this behavior. The approach is inspired by the so-called time-step per based numerical bifurcation theory. We illustrate the approach through the computation of both stable and unstable coarsely invariant states for Kinetic Monte Carlo models of three simple surface reaction schemes. We quantify the linearized stability of these coarsely invariant states, perform pseudo-arclength continuation, detect coarse limit point and coarse Hopf bifurcations and construct two-parameter bifurcation diagrams.Comment: 26 pages, 5 figure

Energy Minimization

The energetic state of a protein is one of the most important representative parameters of its stability. The energy of a protein can be defined as a function of its atomic coordinates. This energy function consists of several components: 1. Bond energy and angle energy, representative of the covalent bonds, bond angles. 2. Dihedral energy, due to the dihedral angles. 3. A van der Waals term (also called Leonard-Jones potential) to ensure that atoms do not have steric clashes. 4. Electrostatic energy accounting for the Coulomb’s Law m protein structure, i.e. the long-range forces between charged and partially charged atoms. All these quantitative terms have been parameterized and are collectively referred to as the ‘force-field’, for e.g. CHARMM, AMBER, AMBERJOPLS and GROMOS. The goal of energy Minimization is to find a set of coordinates representing the minimum energy conformation for the given structure. Various algorithms have been formulated by varying the use of derivatives. Three common algorithms used for this optimization are steepest descent, conjugate gradient and Newton–Raphson. Although energy Minimization is a tool to achieve the nearest local minima, it is also an indispensable tool in correcting structural anomalies, viz. bad stereo-chemistry and short contacts. An efficient optimization protocol could be devised from these methods in conjunction with a larger space exploration algorithm, e.g. molecular dynamics

Symmetry and equivalence restrictions in electronic structure calculations

A simple method for obtaining MCSCF orbitals and CI natural orbitals adapted to degenerate point groups, with full symmetry and equivalnece restrictions, is described. Among several advantages accruing from this method are the ability to perform atomic SCF calculations on states for which the SCF energy expression cannot be written in terms of Coulomb and exchange integrals over real orbitals, and the generation of symmetry-adapted atomic natural orbitals for use in a recently proposed method for basis set contraction

Accelerating crystal plasticity simulations using GPU multiprocessors

Crystal plasticity models are often used to model the deformation behavior of polycrystalline materials. One major drawback with such models is that they are computationally very demanding. Adopting the common Taylor assumption requires calculation of the response of several hundreds of individual grains to obtain the stress in a single integration point in the overlying FEM structure. However, a large part of the operations can be executed in parallel to reduce the computation time. One emerging technology for running massively parallel computations without having to rely on the availability of large computer clusters is to port the parallel parts of the calculations to a graphical processing unit (GPU). GPUs are designed to handle vast numbers of floating point operations in parallel. In the present work, different strategies for the numerical implementation of crystal plasticity are investigated as well as a number of approaches to parallelization of the program execution. It is identified that a major concern is the limited amount of memory available on the GPU. However, significant reductions in computational time – up to 100 times speedup – are achieved in the present study, and possible also on a standard desktop computer equipped with a GPU

Discontinuous Molecular Dynamics for Semi-Flexible and Rigid Bodies

A general framework for performing event-driven simulations of systems with semi-flexible or rigid bodies interacting under impulsive torques and forces is outlined. Two different approaches are presented. In the first, the dynamics and interaction rules are derived from Lagrangian mechanics in the presence of constraints. This approach is most suitable when the body is composed of relatively few point masses or is semi-flexible. In the second method, the equations of rigid bodies are used to derive explicit analytical expressions for the free evolution of arbitrary rigid molecules and to construct a simple scheme for computing interaction rules. Efficient algorithms for the search for the times of interaction events are designed in this context, and the handling of missed interaction events is discussed.Comment: 16 pages, double column revte