CHE 775

Multi-Scale Modeling of Matter

Lecture 13
The Meso-scale - Lattice Monte Carlo
Simulations

Instructor: Keith E. Gubbins

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 Other MC Methods for Phase Equilibria
• There are a number of MC methods that can be used in situations where GEMC
fails:
– Direct interfacial simulation
– Methods to determine chemical potentials (or free energies):
• Thermodynamic integration
• Widom test particle insertion method
• Bennet’s method
For reviews see:
• Non – Boltzmann (umbrella) sampling - D. Frenkel and B. Smit,
– NPT-MC + test particle method Understanding Molecular
– Gibbs – Duhem integration Simulation, 2nd ed., Ch.7-11,
Academic Press (2002)
– Histogram – reweighting - J. J. de Pablo, Q. Yan and
– Pseudo – ensembles F. A. Escobedo, Ann. Rev.
Phys. Chem. 50, 377 (1999)
- A. Z. Panagiotopoulos,
J. Phys.: Condens. Matter 12,
R25 (2000)

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 MC and Phase Equilibria: Indirect Methods
• For situations when GEMC is not suitable, an alternative is to calculate free
energies or chemical potentials for a range of state conditions → indirect
methods. The phase transitions and chemical equilibrium conditions can then be
determined by the usual thermodynamic relationships
• Question: how can we evaluate entropy-related (‘statistical’) quantities, such as
the Gibbs and Helmholtz free energies, the chemical potential and the entropy
itself, in a molecular simulation run?
– It is not possible to measure these functions directly in a simulation
– For example, the expression for A in the NVT ensemble is:

A  kT ln Q N ,V , T 
– Since these functions are related directly to the partition function, not to its
derivatives, they are not simple averages of functions of the phase space
coordinates of the system. To calculate Q would mean summing over all the
possible states of the system (impossible to do in a simulation)

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 Widom’s Test Particle Insertion Method
• There exist several techniques for “measuring” the chemical potential of a given
species in a single MC simulation.
• In these techniques, what we measure is not the chemical potential itself, but the
excess chemical potential, defined as:

μ ex  μ  μ id
where μid is the chemical potential of the given species as an ideal gas under the
same conditions, N,V,T; μid can be evaluated analytically
• A simple method for measuring the excess chemical potential of a species in a
pure fluid or in a mixture is the test particle insertion method proposed by Widom
(B. Widom, J. Chem. Phys. 39, 2808 (1963); J. Phys. Chem. 86, 869 (1982))
• For a derivation of the Widom test particle equation see: C.G. Gray, K.E.
Gubbins, C.G. Joslin, “Theory of Molecular Fluids. 2. Applications”, pp. 633-36,
Oxford University Press (2011)

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 Widom’s Test Particle Insertion Method
• From thermodynamics, we know that μi (the chemical potential of species i) is
defined in the canonical ensemble as:

 A 
i   

 i T ,V , N '
N
Since A  kT ln Q N ,V , T 
 A    ln Q 
i     i   kT   (2)
 N i T ,V , N '  N i T ,V , N '

• For sufficiently large N, we can approximate (2) as (pure substance):

 ln QN 1  ln QN   QN 1 
  kT    kT ln   (3)
  N  1  N   N 
Q
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 Widom’s Test Particle Insertion Method
• In the following derivation, we will assume we have a one-component system with
N atoms* inside a cubic volume V of length L. The canonical partition function of
this system can be written as

(4)

where we have again used the scaled coordinates sN:

ri = Lsi, for i = 1, 2, … N
We have written (sN, L) to indicate that depends on the real coordinates of
the particles in a cubic box of length L, rather than on the scaled distances
between the particles

* The extension to general molecules is straightforward

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 Widom’s Test Particle Insertion Method
• Substituting (4) in (3):

but N + 1 ≈ N
for sufficiently large N
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 Widom’s Test Particle Insertion Method

• But (5)
 V 
μ  ρ   kT ln 3 
id
Λ N  ideal gas reference state
and μ  μ id  μ ex at the same density & temperature
as the system under study

Therefore,
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 Widom’s Test Particle Insertion Method

(6)

• We can rewrite

where test represents the additional interaction energy due to the presence of
the (N+1)th particle (the ‘test’ particle) at an arbitrary fixed point in the box
containing N particles.

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 Widom’s Test Particle Insertion Method

• Therefore, let us rewrite (6) as:

(7)

• But 1

 1
test
d s (scaled coordinates); and canonical average over the
0 configuration space of the
N-particle system

(8)

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 Widom’s Test Particle Insertion Method

(9)
• Equation (9) expresses μex as an ensemble average that can be sampled by the
conventional Metropolis scheme. This equation was called by Widom the
potential distribution theorem. It is valid regardless of the type of molecule or the
presence of multi-body potential terms.
• Algorithm:
– Carry out a conventional NVT-MC simulation on the system with N particles
– At frequent intervals during the simulation, insert a ‘test’ particle in a number
of random positions and compute the interaction of the test particle with all
others. Obtain the average
over the whole run. The test particle is a ‘ghost’ particle. That is, it observes
and measures interactions with the real molecules of the system, but these
real molecules are unaware of the ‘ghost’ particle.

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 Test Particle Method
• For a pure substance: Vapor branch

Coexistence
Chemical potential

Pressure
+
L
 S V
Many simulations
Liquid branch to get one point on
Constant T phase diagram!
Pressure Temperature
or Density
• Need a number of simulations to get one point on phase diagram; tedious search-
and-evaluation process

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 Widom’s Test Particle Insertion Method

• Widom’s method is a very powerful and simple scheme for

computing the chemical potential of atomic and molecular
fluids that are not too dense. It is very general, it does not
rest on (a) pair additivity, (b) spherical molecules – applies to
any kind of molecule, (c) uniform fluids .

• The methodology can be extended to other ensembles.

Equation (9) also applies to the grand canonical ensemble (J.
R. Henderson, Mol. Phys. 50, 741 (1983))

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 Widom’s Test Particle Insertion Method

• For the NPT ensemble, it is necessary to include the

fluctuations in the volume (see K. S. Shing and S. T
Chung, J. Phys. Chem. 91, 1674 (1987); Frenkel &
Smit, pp. 176-177):

(10)

and the ideal gas reference state is now defined at the

same pressure (rather than at the same density, as was
done in the NVT ensemble) as the system under study:

μ id
P   kT lnΛ βP 
3

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 Widom’s Test Particle Insertion Method

• For the NVE ensemble, it is necessary to include the fluctuations in the kinetic
temperature (see D. Frenkel, in Molecular Dynamics Simulations of Statistical
Mechanics Systems, pp. 151-188, ed. G. Ciccotti and W. G. Hoover, Proceedings
of the 97th Int. Enrico Fermi School of Physics, North Holland, Amsterdam
(1986)):

m ex = -k T ln éë T T -3 2 exp ( -U test kT ) ùû
-3 2

• In simulations, it was found that the excess chemical potential is strongly

dependent on the size of the system (see, e.g., U. Heinbruch and J. Fischer, Mol.
Sim. 1, 109 (1987); Frenkel & Smit, p. 178)
• There is an alternative formula which applies to the removal of a test particle
(selected at random) from the system. In practice, this technique does not give an
accurate estimate of the excess chemical potential (see Allen & Tildesley, p. 50;
Frenkel & Smit, p. 179)

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 Widom’s Test Particle Insertion Method

• The Widom method can be modified to measure the

difference in chemical potential between two species i and j
in a mixture; also, a wide class of partial molar quantities
can be measured using this methodology (see Frenkel &
Smit, p. 178)

• As density increases, we need to increase the number of

trial insertions in order to have acceptable statistics. For
very high densities, much higher than 2rc, the number of
trial insertions required becomes unacceptably high and
the method fails.

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 Histogram Reweighting: Free Energies from
Histograms
• In computer simulations, we can adjust our methods to sample from an
unphysical distribution to gather information about the system
• Consider a GCMC simulation, with a fluctuating number of particles. At
equilibrium, the particle number should converge to an average value and
fluctuate about the average
• Because of very low probability of traversing the intermediate density region
between liquid and vapor, the system can get “stuck” and only one phase will be
sampled.
• By introducing a “weighting function” into the Monte Carlo acceptance criteria,
we can reduce the energy barrier and sample more uniformly.
• With this weighting function, we can sample N uniformly and thus sample both
liquid and vapor phases in a single simulation
• This is clearly unphysical (imagine a sample of some substance fluctuating
between liquid and vapor densities), but can give us valuable information about
the system.

M.S. Shell, A. Panagiotopoulos and A. Pohorille, in “Free Energy Calculations”, eds.

C. Chipot and A. Pohorille, Springer-Verlag, Berlin (2007)
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 Free Energies from Histograms
• At normal phase coexistence conditions, the probability of sampling densities
intermediate between liquid and vapor is very low.

• By introducing a “weighting function”, η, into the Monte Carlo acceptance criteria,

we can reduce the energy barrier and sample more uniformly.

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 Free Energies from Histograms
• Adding a weighting function, η(N), to the GCMC acceptance criteria gives state
probabilities:

 U  N  ( N )
 r ,N 
w
 N
 e
 N!
3N

• There are several methods to calculate the weighting function, η(N).

• In the multicanonical method (B. A. Berg and T. Neuhaus, Phys. Rev. Lett. 68, 9
(1992)) the weighting function is calculated iteratively from histograms collected
during individual simulations

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 Free Energies from Histograms
• A simulation is run with a given weighting function (usually initialized as η0(N)=0
and a histogram is collected.
• After this simulation, the weighting function is updated according to

i 1 ( N )  ln f ( N ;i )  i ( N )  k
where f is the number of histogram counts and k is an arbitrary constant usually
assigned to make the minimum of the weighting function zero.

• Iterations continue until the histogram is “flat enough”. If a flat histogram is

achieved, further iterations have no effect on the weighting function, since the
entire function will be shifted by the same amount.

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 Free Energies from Histograms

figure taken from Chipot, Ch, and A. Pohorille. Free Energy Calculations: Theory and Applications in Chemistry and
Biology.
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 Free Energies from Histograms
• Note that the last equation is undefined for a histogram bin with zero counts. It
has been shown (G. R. Smith and A. D. Bruce, J. Phys. A 28, 6623 (1995)) that

i 1 ( N )  ln  f ( N ;i )  1  i ( N )  k
is a statistically-justified update scheme which avoids this difficulty.

• When a flat histogram is achieved, we can estimate the free energy, A(N)

A( N )  N  kT ( N )  constant
• The multicanonical method often has too much statistical error for a direct
calculation of A(N). Other methods are available.

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 Thermodynamic Integration
• References: Frenkel & Smit, pp. 168-172, 241-267 (and references therein); Allen
& Tildesley, pp. 49-50 (and references therein)
• Experiments always determine a derivative of the free energy, e.g.
 A   P
  (11)
 V  N ,T
  A T    
U
  (12)
 T  N ,V T2
• Therefore, to compute the free energy of a system at given temperature and
density, we should find a reversible path in the V-T plane, linking the state under
consideration to a state of known free energy. Then, the change in A along that
path can be evaluated by thermodynamic integration of (11) and (12).
• There are only a few thermodynamic states for which the free energy of a
substance is known. One of them is the ideal gas phase; another is the low-
temperature harmonic crystal.

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 Thermodynamic Integration
• Let us rewrite (11) in terms of the excess Helmholtz free energy:

Aex  ρ   A ρ   Aid  ρ  (13)

where Aid is the Helmholtz free energy of an ideal gas reference state at the same
density and temperature as the system under study. Then,

 Aex   
 
 
id
   
A A
    V    P   P id
 V  N ,T  V  N ,T   N ,T
 Aex 
     P  ρkT  (14)
 V  N ,T

where ρ kT is the pressure of an ideal gas at the same density as the system
under study.

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 Thermodynamic Integration
• Therefore, to determine the Helmholtz free energy of a liquid phase with density
ρ, we can integrate (14) from an ideal gas phase (for which
Aex = 0) to the state of interest, keeping the temperature and N constant:

Aex    1
V
1

d
 0    P   kT  dV    P   kT  2
NkT 
NkT 0
kT 
Aex    A  Aid   
1  P  kT


kT 0  2
      d (15)
NkT NkT NkT 
• An important condition is that the integration path in (15) should be reversible. If
the integration path crosses a first-order transition, hysteresis may occur and (15)
can no longer be used.

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 Thermodynamic Integration
• For a liquid phase at ρ and T, this problem can be avoided by performing the
integration in two steps:
– First, at a temperature TII well above the critical, use (15) to integrate along
this isotherm from the ideal gas phase to the supercritical fluid state at ρ and
TII:

 
 Aid
 ρ  1 ρ
 P  ρkT II  
 NkT II    ρ 2 dρ 
II
A ρ, T II II (16)
 NkT kT 0  

– Then, integrate (12) along a line of constant density, cooling the system from
TII to the temperature of interest T

A ρ, T  A ρ, T II

 U
  2 dT
 T
(17)
II
T T T II
T

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 Thermodynamic Integration
• It is not really necessary to go all the way to the ideal gas. One can start from a
state (ρ1, T1) for which we can compute the free energy. In practice, ρ1 should be
a sufficient low density to ensure that the free energy can be computed accurately
(e.g., by using the Widom method to determine the excess chemical potential).
Then one can determine the Helmholtz free energy of a liquid phase at density ρ2
and temperature T2 by integrating (11):
V2 ρ2
 A    A     PV  dV   P  dρ
   
 NkT  2  NkT 1       2 (18)
V1 
NkT  V ρ1 
kT  ρ
Again, the integration should be done along a reversible path linking the states
(ρ1, T1) and (ρ2, T2).

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 Solid-Liquid Equilibria and Thermo Integration
• The solid-liquid phase equilibria problem requires different approaches. For a
review see, e.g., P. A. Monson and D. A. Kofke, in Advances in Chemical Physics,
ed. I. Prigogine and S. A. Rice, vol. 115, pp.113-179, Wiley, New York (2000).
Also, see Frenkel & Smit, ch. 10
• The main problem is that the solid-liquid coexistence curve itself does not end in
a critical point, and hence there exists no “natural” reversible path from the solid
to the ideal gas that does not cross a first-order phase transition.
• It is usually possible, however, to use thermodynamic integration and construct a
reversible path to other states of known free energy.
• The basic idea of one of the methods is to transform the solid under consideration
reversibly into some reference system for which the free energy can be evaluated
analytically.
• For a brief description of the reference systems used for solids, see the review
paper by Monson & Kofke.

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 Solid-Liquid Equilibria and Thermo Integration
• One of the most widely used reference systems is the non-interacting Einstein
crystal:

“x” marks positions of the non-interacting

particles, which are attached to sites in a
lattice (indicated by the small circles) via
Hookean springs (indicated by the dotted
lines). A simple square lattice is shown for
illustration.
Figure taken from P. A. Monson and D. A. Kofke, in
Advances in Chemical Physics, ed. I. Prigogine
and S. A. Rice, vol. 115, pp.113-179, Wiley, New
York (2000)

• Suppose we have an atomic solid system where the atoms interact with a
continuous potential (rN). We shall use thermodynamic integration to relate the
free energy of this system to that of a non-interacting Einstein crystal (J. Q.
Broughton and G. H. Gilmer, J. Chem. Phys. 79, 5095 (1983); D. Frenkel and A.
J. C. Ladd, J. Chem. Phys. 81, 3188 (1984))

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 Solid-Liquid Equilibria and Thermo Integration
• During the thermodynamic integration, we switch on the spring constants and
switch off the intermolecular interactions. To this end, we consider a potential
energy function:

(19)

where r0,i is the lattice position of atom i and (r0N) is the static contribution to the
potential energy (i.e., the potential energy of a crystal with all atoms at their lattice
positions), λ is the switching parameter and αi is the Einstein-crystal spring
constant coupling atom i to its lattice site.
• Note that for λ = 0 we recover the original interactions. For λ = 1 we have
switched off the intermolecular interactions completely (except for the constant
static term), and the system behaves like an ideal, non-interacting Einstein
crystal.

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 Solid-Liquid Equilibria and Thermo Integration
• The partition function for a system with a potential energy function that
corresponds to a value of λ between 0 and 1 is:

(20)

• The derivative of the Helmholtz free energy A(l) with respect to λ can be written
as an ensemble average:

(21)
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 Solid-Liquid Equilibria and Thermo Integration
where  denotes an ensemble average for a system with a potential energy
λ
function (λ), such as (19).
• Therefore, the free energy difference between the systems with λ = 0 (original
system) and λ = 1 (non-interacting Einstein crystal) can be obtained by integrating
(21):

(22)
• The configurational free energy of the non-interacting Einstein crystal is given by:

where
d = dimensionality (23)

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 Solid-Liquid Equilibria and Thermo Integration

• Important implementation details of this technique (which is

called the Frenkel-Ladd technique) vary with the nature of
the system being studied, including whether the
intermolecular potential is continuous or discontinuous, and
whether the molecules are monatomic or multi-atomic. See
Frenkel & Smit, ch. 10, for a thorough discussion and
implementation details for each one of these cases.

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 The Meso-Scale

Lattice Monte Carlo

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 Outline
• Introduction

• Interaction potentials

• Moves

• Discretization

• Applications

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 The Meso-Scale & Coarse Graining

At the meso-scale we treat matter as made

up of ‘blobs’ (‘beads’), each of which
contains a number of atoms or molecules.
We lose the atomic detail, but speed up the
calculations, enabling us to deal with larger
systems and longer times. This is because
there are fewer pair interactions. Also we
can use longer time steps in MD.
In addition to coarse graining the matter
itself we can coarse grain the space, as in
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 Coarse Graining & Mesoscale: Example, C12E5

Each beads ‘center’ Beads consisting of

is defined as the the same atoms are
center of mass of it’s treated the same
respective atoms

EO EO EO OH
CR1 CR2 CR2 EO EO

CR1: CH3CH2CH2CH2- EO: -CH2CH2O- (ethoxy group)

CR2: -CH2CH2CH2- OH: -CH2CH2OH

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 The Meso-Scale and Coarse Graining

There are many meso-scale methods. All

are approximate and are less rigorous than
the atomistic and electronic scale methods.

Meso-scale methods can give quite good

results for equilibrium properties, including
the meso-scale structure.

They are often poor for transport properties

(e.g., we made the molecules too ‘smooth’).
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 Why Use Lattice MC?
• Can be used to simulate large systems up to
microns or larger; needed for surfactants,
polymers, proteins etc. Off lattice simulations
cannot go much beyond 40-50 nm.

• Can be used to probe equilibrium properties for

processes that require long time scales; e.g. μs
or ms - micelle formation, polymer phase
separation, coil-globule transitions for polymers,
protein folding. Off lattice MD simulations with
large systems cannot go much beyond ~100 -
1000 ns.

• Can be discretized to improve accuracy.

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 Limitations
• Difficult to implement directional contribution to
intermolecular potentials, such as H-bonding.
• In the usual implementation of lattice MC difficult
to include long range forces (e.g. Coulomb).
• Has restrictions on bond angles and lengths.
Only discrete values of bond angles & lengths
are allowed. Entropy affected.
• Quantitative comparison with experimental
results is difficult.
• However, these limitations can be reduced
using recent advances (at a cost!)
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 Simple Lattice Model
Single Polymer chain
molecule
• Molecules occupy discrete positions
inside a lattice.

• A molecule can occupy a single lattice

site, or it can occupy several lattice
sites, as in a polymer chain or
surfactant
• Each molecule attracts or repels a neighboring molecule
depending on the potential energy between them.

• We usually use a square well potential extending to the

nearest and next nearest neighbor, but long range potentials
can be used also.
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 Simple Lattice Model
• Interaction potentials
There are five different types of molecules in
this lattice, A, B, C, D and E.
C B A
eEC
D E The potentials between E and
the neighboring atoms are eEA,
eED eEB, eEC, eED.

eEB eEA
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 Simple Lattice Model
Coordination number, Z

2D - Lattice Z=4 Z=8

3D - Lattice Z=6 Z = 26

In a 2D lattice, E can interact with a maximum of 8 molecules.

Therefore, the coordination number is 8. In a 3D lattice, the
maximum coordination number is 8+9+9=26.

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 Simple Lattice Model
Lattice simulation: Discontinuous potential
-2 1 -2 1
-1.5 -1.5
Reduced Potential

Reduced Potential
-1 Square well -1
-0.5 -0.5
0 0
0.5 0.5
1 Long range potential 1
1.5 used by 1.5
2
0 0.5 1 1.5 2 2.5 3 Panagiotopoulos 2
0 0.5 1 1.5 2 2.5 3
Reduced distance Reduced distance

Off lattice simulation: Continuous potential

0.4 4*((1/x)**12-(1/x)**6)

0.2
Reduced Potential

0
-0.2
-0.4 Lennard-Jones
-0.6 potential
-0.8
-1
-1.2
0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4
Reduced distance
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 Simple Lattice Model
• Effective interaction parameter: 2 Species
A lattice system containing two types of molecules with
different interaction potentials can be represented by a
single effective interaction parameter.

Imagine a system in the NVT ensemble containing two

different types of particles, A and B.
The number of A particles: NA, number of B particles: NB

Therefore, N A  NB  N (1)

Let the number of A-A contacts be NAA, number of B-B

contacts, NBB and number of A-B contacts, NAB

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 Simple Lattice Model
• Effective interaction parameter
E is the total energy of the system for a given configuration.
EN e N e N e
AA AA BB BB AB AB
(2)

For a change to a new configuration, the change in E is ∆E.

E  N AAeAA  N BBeBB  N ABeAB (3)

Let the coordination number be z, so that

zN A  2N AA  N AB and zNB  2NBB  N AB (4)

For a change to a new configuration, zNA and zNB remain fixed,

so 1 1
N AA   N AB and N BB   N AB (5)
2 2 NC STATE UNIVERSITY
 Simple Lattice Model
• Effective interaction parameter
Substituting (5) in (3), we get
1 1
E  N AB (eAB  eAA  eBB ) (6)
2 2
wAB

wAB is called the effective interaction parameter.

When the system assumes a new configuration, the change in

energy ∆E and hence the probability of occurrence of the new
configuration is dependent on wAB, not the individual potentials.

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Effective Interaction Parameters

Effective interaction parameter: 3 Species

This is easily generalized to more components.

For 3 components, A, B and C there will be one
effective interaction parameter for each pair:

DE = DN AB wAB + DN AC wAC + DN BC wBC

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 Simulation scheme
1. A molecule (chain / solvent) is chosen
randomly.
2. The molecule is moved to a new position.
3. The energy of the new configuration is
calculated.
4. The move is accepted according to the
canonical acceptance probability,
é æ DE ö ù
Pacc = min ê1,exp ç - ÷ ú
ë è kT øû
E  Enew  Eold T: temperature, k: Boltzmann factor
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 Moves
Moves are employed to change the positions
of the molecules during simulation.

Single molecules can be moved using

1. Switch
Polymer chains can be moved using
1. Reptation
2. Twist
3. Regrowth using Configurational Bias

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 Switch
Two solvent molecules exchange positions

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 Reptation
Each segment of a chain is moved through
one lattice unit, in a snake-like motion.

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 Twist
A single segment is moved through one
lattice unit keeping the rest of the chain fixed.

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 Chain regrowth: Configurational bias
The entire chain or a part of the chain is
grown in a different part of the box.

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 Configurational Bias

J.I. Siepmann, “A Method for the Direct

Calculation of Chemical Potentials for
Dense Chain Systems”, Molecular Physics,
70, 1145 (1990); J.I. Siepmann and
D. Frenkel, Mol. Phys., 75, 59 (1992).
Ilja Siepmann, Univ. Minnesota
Attempting to make a Monte Carlo move of a chain of n mers is not feasible
using standard MC moves. For a liquid-like density, the probability of
acceptance of an insertion attempt for a single mer is about 0.5%, i.e. 1
out of 200 attempted moves is accepted. If you try to insert n mers, the
probability of acceptance is only 1 in 200n. So for a 8 member chain this
is only 1 successful insertion for every 1018. Clearly this is not practical.
The configurational bias method dramatically improves the odds of
acceptance of each mer by ‘growing’ the chain molecule through adding
mers in a preferentially directed (i.e. biased) way that is more likely to
lead to successful insertion. The method can be applied to both lattice
MC and off-lattice MC simulations.
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Chain regrowth: Configurational bias algorithm
Ref: Frenkel & Smit, “Understanding Molecular Simulation”, Ch. 13; Leach, Sec.
8.11: Appendix to these slides
1. Insert the first segment randomly
2. Compute w1 (n)  z  exp  u1 (n) / kT 
z: coordination no., u1(n): energy of the
first segment (here n = new config.).
3. In turn, insert the second segment in all z
positions adjacent to the first atom.
Calculate z
 u2 ( j ) 
w2 (n)   exp  
j 1  kT 
u2(j): energy of second segment in jth position
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 Chain regrowth: Configurational bias

4. Insert the second atom in one of the z

positions according to prob. P2(n)
exp  u2 (n) / kT 
P2 (n) 
w2 (n)
5. Repeat for all the segments.
6. Calculate Rosenbluth Factor W(n) of the
new configuration l
W (n)   wi ( n)
i 1
l: chain length (no. of chain segments)
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 Chain regrowth: Configurational bias

7. Calculate Rosenbluth Factor W(o) of the

old configuration.
8. Accept the trial move with a probability
 W ( n) 
Pacc  min  ,1
 W (o ) 

9. See Appendix for more details and

derivation

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 Lattice Discretization

Normal lattice Discretized lattice

• Qualitative comparisons • Quantitative comparisons

possible possible

A. Z. Panagiotopoulos, J. Chem Phys, 112(16), 7132 (2000)

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 Discretization

Lattice Discretization parameter: 

Particle diameter
 
Lattice size

1 2 3 4 5

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 Discretization
Comparison of discretized lattice with off-lattice simulations1:
Gas-Liquid Phase Coexistence of + 1
Lennard-Jones particles

x 2

Increasing 3

 5

  10

Off-lattice
line simulation

Ref: 1) A. Z. Panagiotopoulos, J. Chem Phys, 112(16), 7132 (2000)

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 Applications

Lattice MC has various applications in simulations of

• Surfactant solutions
 Surfactant / water
 Surfactant / Water /oil

• Supercritical fluids

• MCM, MCF materials

• Polymers

• Proteins

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 Applications
Larson’s model of surfactant solutions:

• Simple cubic lattice

• Fully occupied

• Coordination number, Z = 26

• Site interacts with all its neighbors

w12  12  11   22 

1
• Single energy parameter
2

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Ron Larson, University of Michigan

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 Applications: Larson’s model
Binary system – Water/Surfactant
Simulation1 Experiment2

H4T4 surfactant in Water Lithium perfluorooctanoate in water

• Simulation and experiment are qualitatively (somewhat!) similar

Ref: 1) R. G.Larson, J. Chem. Phys, 96(11), 7904 (1992)

2) P. Kekicheff, G. J. T. Tiddy, J. Phys. Chem, 93, 2520 (1989)
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 Applications: Larson’s model
Ternary system – Water/Oil/Surfactant
Simulation1 Experiment2

H4T4 surfactant/ Oil/ Water

Sodium-1-tetradecanoate/ 1-decanol/ water

• We notice significant discrepancies between simulation and experiment

• Need to extend the simple lattice model

Ref: 1) R. G.Larson, J. Phys II, 6, 1441, (1996)

2) P. K. Kilpatrick, J. C. Blackburn, and T. A. Walter, 8, 2192 (1992)
NC STATE UNIVERSITY
 Applications: Surfactant Solutions
Some interesting results in surfactant solutions
using Lattice MC :

• A drop in free monomer concentration with increasing total

surfactant concentration above CMC in contrast to equilibrium
theories1

• Characterization of size and shape distributions of micelles1,2

• Thermodynamic properties of micelles3,4

• Spontaneous vesicle formation5

Ref: 1) A.D. Mackie and A.Z. Panagiotopoulos, Langmuir 13, 5022 (1997).
2) P.H. Nelson, G.C. Rutledge and T.A. Hatton, J Chem Phys 107, 10777 (1997)
3) M.A. Floriano and E. Caponetti, Langmuir 15, 3143 (1999)
4) C.M. Care and T. Dalby, Europhys Lett 45, 38 (1999)
5) A.T. Bernardes, Langmuir 12, 5763 (1996)
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 Applications: Supercritical Fluids
Model
Supercritical Fluids:
Surfactant
Surfactant in supercritical Vacancy
CO2
CO2
Vacancies to account for CO2 compressibility

Surfactants Micelles

Surfactant
Conc.

(< CMC) (> CMC)

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 Applications: Supercritical Fluids
Qualitative comparison with experiment: Surfactants in supercritical CO2
Simulation1 Experiment2

H5T4 surfactant in scCO2 PVAC-b-PTAN surfactant in scCO2

Ref: 1) Lauriane F. Scanu, Keith E. Gubbins, and Carol K. Hall, Langmuir, 20 (2), 514-523 (2004)
2) E. Buhler, A. V. Dobrynin, J. M. Desimone, and M. Rubinstein, Macromolecules, 31, 7347 (1998)
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 Applications: Mesoporous Materials
Synthesis of MCM-41
Surfactant Silica 9600 surfactant chains
17400 silica units
Reduced temperature 6.5

-130
-132

-134

Energy per molecule

-136

-138
-140

-142 Equilibrium
-144
-146
-148
0 100000 200000 300000 400000 500000
cycles

Ref: 1) F. R. Siperstein, K. E. Gubbins, Langmuir, 19, 2049(2003)

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 Applications: Mesoporous Materials (MCF)
Synthesis of Mesostructured Cellular Foam
window cell cell

window
Structure obtained by
Lattice MC

Computer Schematic

Pore size distribution

Transmission Electron Microscopy

S. Bhattacharya and K.E. Gubbins, “Modeling Triblock Surfactant-Templated Mesostructured Cellular
Foams” J Chem. Phys. 123, 134907 (2005). NC STATE UNIVERSITY
 Applications: Surfactant Adsorption

T=0.9 Simulation
1 Experiment2

45OC 25OC 5OC

T=1.3
Adsorption of HT2 on H-preferred surface1 C8E4 in controlled pore glass (CPG-10, 24 nm)2

• Opposite temperature dependency in simulations compared to experiments

• Shows the inadequacy of simple interaction potentials and the need to
include hydrogen bonding in the model
Ref: 1) U. Reimer, M. Wahab, P. Schiller, H.-J. Mögel, Langmuir, 17, 8444 (2001)
2) R. Dabiri and G.H. Findenegg, personal communication (2002)
3) H. Bock and K.E. Gubbins, Phys. Rev. Letters, 92, 135701 (2004)
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 Applications: Confined polymers
Diblock Copolymer confined between heterogeneous substrates
Simulation1 Experiment2

Confined PS-b-PMMA
Confined H12T12 copolymer copolymer
• Similar structures found in experiments and simulations
• Simulation also predicts other structures depending on Pattern spacing LS

Ref: 1) Q. Wang, Q. Yan, P. F. Nealey, and J. J. de Pablo, Macromolecules, 33, 4512 (2000)
2) L. Rockford, Y. Liu, P. Mansky, T. P. Russell, M. Yoon and S. G. J. Mochrie, Phys. Rev. Lett. 82, 2602(1999)
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 2-D Lattice model of the separation of water/protein mixture

Figure 1. Model protein and water. The black circles Figure 2. Phase diagram of a 20-mer homopolymer
represent protein monomers, and the lines protein calculated using the combined protein and
connecting them are covalent bonds. The white and water simulation(solid line) and the separated protein
gray circles are bulk and interfacial water molecules, in vacuo simulation (dashed line). Temperature and
respectively. The four arms on each water molecule pressure are presented in dimensionless units.
are the hydrogen bonding arms. Two examples are
shown of interfacial bonding arm pairs, which involve
at least one interfacial water molecule. Debenedetti PG et al., JPCA, 111, 12651, 2007.
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 Appendix: Configurational Bias Method
Acceptance Criteria: Derivation
Detailed balance:
Po  P(o  n)  Pacc  Pn  P(n  o) (7)

P0, Pn: probability of old, new configuration,

exp(U o / kT ) exp(U ch (o) / kT )  exp(U rest / kT )(8)

Po  
Q Q
Uo(Box energy)=Uch(o)(Chain)+Urest(Rest of box)

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Chain regrowth: Configurational bias
Probability of change from old to new:
P(o  n)  P1 (n)  P2 (n)  .........Pl (n)
 exp(u2 (n) / kT ) 
 z   exp(u1 (n) / kT )    
 w2 ( n ) 
 exp(ul (n) / kT ) 
...........   (9)
 w l ( n ) 
exp(U ch (n) / kT )
 z
W ( n)
Similarly, P(n  o)  z  exp(U ch (o) / kT ) (10)
W ( o)

and exp(U ch (n) / kT )  exp(U rest / kT ) (11)

Pn 
Q
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Chain regrowth: Configurational bias
Substituting (8), (9), (10) and (11) in
(7), we get
 W ( n) 
Pacc  min  ,1
 W (o ) 

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