113 research outputs found
Targeted free energy perturbation
A generalization of the free energy perturbation identity is derived, and a
computational strategy based on this result is presented. A simple example
illustrates the efficiency gains that can be achieved with this method.Comment: 8 pages + 1 color figur
Multicanonical Multigrid Monte Carlo
To further improve the performance of Monte Carlo simulations of first-order
phase transitions we propose to combine the multicanonical approach with
multigrid techniques. We report tests of this proposition for the
-dimensional field theory in two different situations. First, we
study quantum tunneling for in the continuum limit, and second, we
investigate first-order phase transitions for in the infinite volume
limit. Compared with standard multicanonical simulations we obtain improvement
factors of several resp. of about one order of magnitude.Comment: 12 pages LaTex, 1 PS figure appended. FU-Berlin preprint FUB-HEP 9/9
Model of a fluid at small and large length scales and the hydrophobic effect
We present a statistical field theory to describe large length scale effects
induced by solutes in a cold and otherwise placid liquid. The theory divides
space into a cubic grid of cells. The side length of each cell is of the order
of the bulk correlation length of the bulk liquid. Large length scale states of
the cells are specified with an Ising variable. Finer length scale effects are
described with a Gaussian field, with mean and variance affected by both the
large length scale field and by the constraints imposed by solutes. In the
absence of solutes and corresponding constraints, integration over the Gaussian
field yields an effective lattice gas Hamiltonian for the large length scale
field. In the presence of solutes, the integration adds additional terms to
this Hamiltonian. We identify these terms analytically. They can provoke large
length scale effects, such as the formation of interfaces and depletion layers.
We apply our theory to compute the reversible work to form a bubble in liquid
water, as a function of the bubble radius. Comparison with molecular simulation
results for the same function indicates that the theory is reasonably accurate.
Importantly, simulating the large length scale field involves binary arithmetic
only. It thus provides a computationally convenient scheme to incorporate
explicit solvent dynamics and structure in simulation studies of large
molecular assemblies
Multi-Overlap Simulations for Transitions between Reference Configurations
We introduce a new procedure to construct weight factors, which flatten the
probability density of the overlap with respect to some pre-defined reference
configuration. This allows one to overcome free energy barriers in the overlap
variable. Subsequently, we generalize the approach to deal with the overlaps
with respect to two reference configurations so that transitions between them
are induced. We illustrate our approach by simulations of the brainpeptide
Met-enkephalin with the ECEPP/2 energy function using the global-energy-minimum
and the second lowest-energy states as reference configurations. The free
energy is obtained as functions of the dihedral and the root-mean-square
distances from these two configurations. The latter allows one to identify the
transition state and to estimate its associated free energy barrier.Comment: 12 pages, (RevTeX), 14 figures, Phys. Rev. E, submitte
Spin glass overlap barriers in three and four dimensions
For the Edwards-Anderson Ising spin-glass model in three and four dimensions
(3d and 4d) we have performed high statistics Monte Carlo calculations of those
free-energy barriers which are visible in the probability density
of the Parisi overlap parameter . The calculations rely on the
recently introduced multi-overlap algorithm. In both dimensions, within the
limits of lattice sizes investigated, these barriers are found to be
non-self-averaging and the same is true for the autocorrelation times of our
algorithm. Further, we present evidence that barriers hidden in dominate
the canonical autocorrelation times.Comment: 20 pages, Latex, 12 Postscript figures, revised version to appear in
Phys. Rev.
Phase Behavior of Bent-Core Molecules
Recently, a new class of smectic liquid crystal phases (SmCP phases)
characterized by the spontaneous formation of macroscopic chiral domains from
achiral bent-core molecules has been discovered. We have carried out Monte
Carlo simulations of a minimal hard spherocylinder dimer model to investigate
the role of excluded volume interations in determining the phase behavior of
bent-core materials and to probe the molecular origins of polar and chiral
symmetry breaking. We present the phase diagram as a function of pressure or
density and dimer opening angle . With decreasing , a transition
from a nonpolar to a polar smectic phase is observed near ,
and the nematic phase becomes thermodynamically unstable for . No chiral smectic or biaxial nematic phases were found.Comment: 4 pages Revtex, 3 eps figures (included
Lattice-switch Monte Carlo
We present a Monte Carlo method for the direct evaluation of the difference
between the free energies of two crystal structures. The method is built on a
lattice-switch transformation that maps a configuration of one structure onto a
candidate configuration of the other by `switching' one set of lattice vectors
for the other, while keeping the displacements with respect to the lattice
sites constant. The sampling of the displacement configurations is biased,
multicanonically, to favor paths leading to `gateway' arrangements for which
the Monte Carlo switch to the candidate configuration will be accepted. The
configurations of both structures can then be efficiently sampled in a single
process, and the difference between their free energies evaluated from their
measured probabilities. We explore and exploit the method in the context of
extensive studies of systems of hard spheres. We show that the efficiency of
the method is controlled by the extent to which the switch conserves correlated
microstructure. We also show how, microscopically, the procedure works: the
system finds gateway arrangements which fulfill the sampling bias
intelligently. We establish, with high precision, the differences between the
free energies of the two close packed structures (fcc and hcp) in both the
constant density and the constant pressure ensembles.Comment: 34 pages, 9 figures, RevTeX. To appear in Phys. Rev.
Constraint methods for determining pathways and free energy of activated processes
Activated processes from chemical reactions up to conformational transitions
of large biomolecules are hampered by barriers which are overcome only by the
input of some free energy of activation. Hence, the characteristic and
rate-determining barrier regions are not sufficiently sampled by usual
simulation techniques. Constraints on a reaction coordinate r have turned out
to be a suitable means to explore difficult pathways without changing potential
function, energy or temperature. For a dense sequence of values of r, the
corresponding sequence of simulations provides a pathway for the process. As
only one coordinate among thousands is fixed during each simulation, the
pathway essentially reflects the system's internal dynamics. From mean forces
the free energy profile can be calculated to obtain reaction rates and insight
in the reaction mechanism. In the last decade, theoretical tools and computing
capacity have been developed to a degree where simulations give impressive
qualitative insight in the processes at quantitative agreement with
experiments. Here, we give an introduction to reaction pathways and
coordinates, and develop the theory of free energy as the potential of mean
force. We clarify the connection between mean force and constraint force which
is the central quantity evaluated, and discuss the mass metric tensor
correction. Well-behaved coordinates without tensor correction are considered.
We discuss the theoretical background and practical implementation on the
example of the reaction coordinate of targeted molecular dynamics simulation.
Finally, we compare applications of constraint methods and other techniques
developed for the same purpose, and discuss the limits of the approach
Adsorption of mono- and multivalent cat- and anions on DNA molecules
Adsorption of monovalent and multivalent cat- and anions on a deoxyribose
nucleic acid (DNA) molecule from a salt solution is investigated by computer
simulation. The ions are modelled as charged hard spheres, the DNA molecule as
a point charge pattern following the double-helical phosphate strands. The
geometrical shape of the DNA molecules is modelled on different levels ranging
from a simple cylindrical shape to structured models which include the major
and minor grooves between the phosphate strands. The densities of the ions
adsorbed on the phosphate strands, in the major and in the minor grooves are
calculated. First, we find that the adsorption pattern on the DNA surface
depends strongly on its geometrical shape: counterions adsorb preferentially
along the phosphate strands for a cylindrical model shape, but in the minor
groove for a geometrically structured model. Second, we find that an addition
of monovalent salt ions results in an increase of the charge density in the
minor groove while the total charge density of ions adsorbed in the major
groove stays unchanged. The adsorbed ion densities are highly structured along
the minor groove while they are almost smeared along the major groove.
Furthermore, for a fixed amount of added salt, the major groove cationic charge
is independent on the counterion valency. For increasing salt concentration the
major groove is neutralized while the total charge adsorbed in the minor groove
is constant. DNA overcharging is detected for multivalent salt. Simulations for
a larger ion radii, which mimic the effect of the ion hydration, indicate an
increased adsorbtion of cations in the major groove.Comment: 34 pages with 14 figure
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