Molecular Simulation Methods Final Project

(Course code: ChE562e)

Project Title:
Select one state point of LJ fluid comparing the
simulation results obtained NVT and NPT MC Simulations (for
example, density and pressure obtained)

Submitted to:
Dr. Qingyuan yang

Submitted By:
Muhammad Mudassar Aslam

Student ID:
2014220016

Date:
2016-12-26
Abstract
Monte Carlo Simulation on lennard-Jones fluid (Methane CH4) is carried out in python software
for Isothermal-Isochoric (NVT) and Isothermal-Isobaric (NPT) system. Simulations was run in a
hard cubic sphere. The system becomes thermodynamically equilibrium after 2 million trial moves
and next 2 million trial moves for calculations. The results for energy change, reduced density,
reduced pressure, heat capacity, Trial Move Acceptance ratio are discussed in this article

Introduction
J.K. Johnson, et al. [1] investigated the Lennard-Jones equation of state with Molecular Dynamics
simulations over a range of temperature, density and steps. However, we do observe an increase
in pressure with an increase in density, as expected. The obtained values of pressure and density
in the current simulation is different from that reported by J.K. Johnson. In the current simulation,
Monte Carlo was chosen over Molecular Dynamics because of the different temperatures and
pressure parameters that is possible with a canonical ensemble (NVT or NPT).

Monte Carlo Simulations in Two Ensembles

There are several popular ensembles for MC simulations, categorized by different thermodynamic
constraints. Canonical ensemble (NVT) [2] refers to all states consistent with fixed temperature,
volume and number of particles. Grand canonical ensemble (µVT) refers to the system with fixed
volume, temperature and chemical potential, which can be used to compute the average molecule
number in adsorption studies. Isobaric-isothermal ensemble (NPT) is constrained by constant
pressure, temperature and number of molecules. Gibbs-NVT ensemble accounts for the phase
equilibrium with constant temperature, volume and number of particles. Gibbs-NPT ensemble
deals with systems under constant temperature, pressure and number of molecules for phase
equilibrium. In this chapter, NPT ensemble and Gibbs-NPT ensemble will be introduced. [3]
As is usually the case, temperature, density (number density), pressure, etc., are given in reduced
units (denoted by *). That is, these properties are expressed in terms of the characteristic energy,
ε, and length scale, σ, defined by the Lennard-Jones potential:
VLJ(r) = 4 ε [ (σ/r)12 - (σ/r)6]
For computational expediency, the potential and force are usually truncated at some cutoff distance
rc. That is, the effective potential V(r) is

In this work, the cutoff distance is taken to be 3σ, unless noted otherwise. An approximate
correction for this truncation to the energy and pressure of the system can be obtained by assuming
the spatial correlations beyond the cutoff distance are unity. The reader is referred to Refs. [4] And
[5] for these so-called “standard long range corrections” (sLRC). It should be noted that this not a
good assumption in inhomogeneous fluids. For completeness, the working expressions for
obtaining the long range corrections to the potential energy per particle and virial pressure are
provided below:

Where ρ is the bulk number density, VLJ(r) is the Lennard-Jones potential energy, and rc is the
truncation (cutoff) distance. A subtle point to note is that the above pressure correction does not
account for impulsive effects at rc where the potential energy (and therefore the force) changes
discontinuously. This is particularly important when trying to simulate directly interfacacial
phenomena [6]. Finally, it should be mentioned that other truncation and long range correction
schemes for dealing with non-bonded interactions exist. In some cases, the truncation schemes can
yield critical properties that differ from those quoted above.

Monte Carlo NVT simulation of LJ fluid

Simulation of a box of Lennard-Jones fluid (Metahne CH4) particles using Monte Carlo method.
The potential energy and pressure at varying parameters of temperature and density. Parameters
set for Simulation are:
No. of particles = 25
Number of atoms: 25
Epsilon: 166.78
Sigma: 3.678
Cut of distant is 2.5.
Number of Trial Moves: 4000000
Number of Equilibration Steps: 200000
The simulation run was started at random atomic positions, at reduced temperature (T*) of 0.90,
0.95, 1.0, 1.05 and reduced density (ρ*) 0.1, 0.3, 0.5, 0.7, 0.9 at random initial configuration (istart
value). Lennard jones parameters for methane CH4 are ε = 166.78, σ = 3.678. [8]

Figure 1: Equation of stat Lennard Jones fluid isotherm at T=0.9, 0.95, 1.0, 1.05 for Monte Carlo NVT simulation

Figure 1 shows Reduced pressure increased with reduced density at different temperature of NVT
simulation.
 NVT T* VS P*
3.50E-05

3.00E-05
Reduced
2.50E-05 density
0.
2.00E-05
9
P*

1.50E-05 0.
7
1.00E-05 0.
5
5.00E-06

0.00E+00
0.9 0.95 1 1.05
T*

Figure 2: Graph between reduce temperature and reduced pressure at different reduced densities for MC simulation for CH 4
lennard jones fluid

In figure 2 reduced pressure increased slightly at different reduce temperature but pressure
increased with increasing reduced densities

Figure 3: reduced density Vs. Energy for MC NVT simulations

Figure 3 shows after equilibrium Energy of the system decreases with increasing reduced density
and becomes constant.
 NVT
0.08
TRIAL MOVE ACCEPTANCE RATIO

0.075
0.07
Density = 0.1
0.065
0.06 Density = 0.3
0.055 Density = 0.5
0.05
0.045 Density = 0.7
0.04 Density = 0.9
0.85 0.9 0.95 1 1.05 1.1
T*

Figure 4: plot between reduced temperature and Trial move acceptance ratio

Figure 4 shows the acceptance ratio for different trial moves. Trial move acceptance ratio decreases
with increase in temperature but varying densities have not much effect.
A table for energies, heat capacity and acceptance ratio for Monte Carlo NVT simulations is shown
below
Table 1: results of different MC NVT simulation

T* ρ* Energy Energy Cv P* Acceptance

kcal/mol Squared Ratio
0.90 0.1 -398.578 202731.8 0.003938 1.07 x 10-06 0.07407
0.90 0.3 -420.883 226875.1 0.004338 3.21 x 10-06 0.073249
0.90 0.5 -413.94 219695.5 0.004393 5.34 x 10-06 0.073643
0.90 0.7 -402.742 206521.8 0.003937 7.48 x 10-06 0.073652
0.90 0.9 -417.033 226835.5 0.004514 9.62 x 10-06 0.073621
0.95 0.1 -401.354 208987.8 0.003833 1.13 x 10-06 0.062962
0.95 0.3 -398.95 203723.5 0.003493 3.38 x 10-06 0.063177
0.95 0.5 -399.373 205213 0.003564 5.64 x 10-06 0.063166
0.95 0.7 -402.883 211454.9 0.003856 7.89 x 10-06 0.063054
0.95 0.9 -399.603 206123 0.003802 1.02 x 10-05 0.063052
1.0 0.1 -391.922 198754 0.003085 1.19 x 10-06 0.054493
1.0 0.3 -389.519 197010.3 0.003036 3.56 x 10-06 0.054539
1.0 0.5 -382.9 189110.8 0.002975 5.94 x 10-06 0.054607
1.0 0.7 -382.8 190264.6 0.003174 8.31 x 10-06 0.054561
1.0 0.9 -385.738 193052 0.003206 1.07 x 10-05 0.054716
1.05 0.1 -363.712 171144 0.002506 1.25 x 10-06 0.047702
1.05 0.3 -368.24 177207.8 0.002575 3.74 x 10-06 0.047774
1.05 0.5 -374.705 182474.5 0.002705 6.23 x 10-06 0.047557
1.05 0.7 -365.142 173526.2 0.002554 8.73 x 10-06 0.04769
1.05 0.9 -376.754 184157.5 0.002723 1.12 x 10-05 0.047512
Monte Carlo NPT simulation of LJ fluid
Simulation of a box of Lennard-Jones fluid (Metahne CH4) particles using Monte Carlo method.
The potential energy and density at varying parameters of temperature and pressure
Number of atoms: 25
Epsilon: 166.78
Sigma: 3.678
Cut of distant is 2.5
Number of Trial Moves: 4000000
Number of Equilibration Steps: 2000000
The interval to collect data after equilibration: 100
The simulation run was started at random atomic positions, at reduced temperature (T*) of 0.90,
0.95, 1.0, 1.05 and reduced Pressure (P*) 1.0, 3.0, 5.0, 7.0, 9.0 at random initial configuration
(istart value). Lennard jones parameters for methane CH4 are ε = 166.78, σ = 3.678. [8]

NPT
10

6 T* = 0.90
P*

4 T* = 0.95
T* = 1.0
2
T* = 1.05
0
0 1 2 3 4
REDUCED DENSITY

Figure 5: Equation of stat Lennard Jones fluid isotherm at T=0.9, 0.95, 1.0, and 1.05 for Monte Carlo NPT simulation

Figure 5 shows with increasing pressure increased density increases at different temperature for
NPT simulation. In simulation in NPT simulation reduced pressure is bigger than NVT simulation
at different reduced densities
Figure 6: Plot between Reduced temperature and reduced density for MC NPT Simulation

Figure 5 shows with increasing temperature density of fluid decreases but with increasing pressure
density increases

Figure 7: reduced temperature Vs. Volume for NPT simulation

Figure7 shows with increase in temperature volume of the fluid increases and with increase in
pressure volume decreases. At reduced pressure 1 volume is much bigger in the range of 3400 to
4000 but at pressure 3,5,7,7 volume is lower in than 1000.

Figure 8:Energy of lennard jones fluid particles vs. pressure graph at different temperature for MC NVT simulation

A table for energies, heat capacity and acceptance ratio for Monte Carlo NVT simulations is
shown below

NPT
0.9
TRIAL MOVE ACCCEPTANCE RATIO

0.8
0.7
0.6
P* = 1.0
0.5
P* = 3.0
0.4
P* = 5.0
0.3
P* = 7.0
0.2
0.1 P* = 9.0

0
0.85 0.9 0.95 1 1.05 1.1
T*

Figure 9: Plot between Reduced temperature and trial move acceptance ratio at different pressure for MC lj NVT simulation

Figure 9 shows acceptance ratio for trial move at different temperature and pressure varies with
T* and P*. In MC LJ NVT acceptance ratio decreases with increase in temperature.
Table 2: results of different MC NPT simulation

T* P* Energy Enthalpy Heat ρ* Volume Acceptance

Kcal/mol Capacity Of box Ratio
0.90 1.0 -1696.17 1730.403 0.070907 0.380329 3426.568 0.739676
0.90 3.0 -6208.01 -3816.64 0.240535 1.655174 797.1213 0.487455
0.90 5.0 -7471.7 -4841.5 0.182194 2.456011 526.0401 0.412375
0.90 7.0 -8116.81 -5115.64 0.172371 3.002741 428.7386 0.375266
0.90 9.0 -8499.41 -5159.72 0.142489 3.448101 371.077 0.348626
0.95 1.0 -1757.88 1665.444 0.106531 0.394891 3423.325 0.767656
0.95 3.0 -5444.61 -2779.84 0.201241 1.462849 888.2554 0.520955
0.95 5.0 -6913.85 -4020.73 0.187679 2.250502 578.6239 0.433126
0.95 7.0 -7677.76 -4513.08 0.149916 2.839871 452.0964 0.384982
0.95 9.0 -8092.31 -4570.71 0.134256 3.277277 391.2886 0.35764
1.0 1 -1348.98 2575.604 0.084017 0.328148 3924.583 0.783761
1.0 3 -4918.21 -2014.78 0.178506 1.353398 967.8099 0.543761
1.0 5 -6352.79 -3199.4 0.193773 2.067134 630.6765 0.450552
1.0 7 -7204.16 -3775.95 0.165012 2.633342 489.7437 0.400321
1.0 9 -7601.48 -3809.6 0.147785 3.04566 421.3197 0.367004
1.05 1 -1374.87 2515.931 0.0943 0.341832 3890.798 0.776918
1.05 3 -4155.79 -785.634 0.218247 1.179121 1123.385 0.578759
1.05 5 -5809.8 -2389 0.181389 1.903982 684.1602 0.470351
1.05 7 -6676.45 -2976.29 0.169934 2.443472 528.5943 0.413056
1.05 9 -7243.32 -3244.66 0.149386 2.889195 444.2963 0.374936

Conclusions:
I have presented MC simulation results for LJ fluid Methane at different state over a wide range
of temperature and density.
parameters for the equation of state for the LJ fluid have been studied for the temperature range
0.90, 0.95, 1.0, 1.05 and covering densities 0.1, 0.3, 0.4, 0.5, 0.7, 0.9. Performed calculations on
one state point to calculate energy of methane atoms for Monte Carlo NVT and NPT simulations.
System becomes equilibrium state afte 2 million steps and for next 2 million steps calculated
Potential Energies and heat capacities for both NVT and NPT. The probability of moving a single
particle or a cluster is dependent on local force fields. MC techniques require one to choose the
size step of local the MC displacement
References:

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state revisited, Molecular Physics, 78:3, 591-618, DOI:10.1080/00268979300100411
[2] S. Nosé, “A Molecular dynamics method for simulations in the canonical ensemble,”
Molecular Physics, vol.52, no. 2, pp. 225-268, 1984
[3] D. Adams, “Grand canonical ensemble monte carlo for a lennard-jones fluid,” Molecular
Physics, vol. 29, no. 1, pp.307-311, 1975
[4] M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Oxford University Press,
New York, 1989)
[5] D. Frenkel and B. Smit, Understanding Molecular Simulation, 2nd ed. (Academic, San Diego,
2002)., pp.37-38.
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[8] Liong Seng Tee, Sukehiro Gotoh and Warren E. Stewart. Molecular Parameters for Normal
Fluids. The Lennard-Jones 12-6 Potential