CE 530 Molecular Simulation
CE 530 Molecular Simulation
CE 530 Molecular Simulation
Multi-Scale Modeling
Continuum
Methods
Time/s
100
Atomistic
Simulation
Methods
(ms) 10-3
Mesoscale methods
Lattice Monte Carlo
Brownian Dynamics
Dissipative Particle Dynamics
(s) 10-6
(ns) 10-9
(ps) 10-12
Semi-empirical
methods
Ab initio
methods
Tight-binding
MNDO, INDO/S
(fs) 10-15
10-10
10-9
10-8
10-7
(nm)
10-6
10-5
10-4
(m)
Length/m
F.R. Hung, K.E. Gubbins, and S. Franzen, Chemical Engineering Education, Fall 2004
Pros
Cons
Pros
Cons
Pros
Cons
Meso-Scale Modeling
Basic idea
Average out faster degrees of freedom and/or treat large groups
of atoms as single entities with effective interactions.
Pros
Cons
Continuum Modeling
Basic idea
Assume that matter is continuous and treat system properties as
fields. Numerically solve balance and constitutive equations.
Pros
Cons
Requires specification of
constitutive model
Requires data from experiment
or lower-level method
Cannot explain molecular
origins of behavior
Multi-Scale Modeling
Continuum
Methods
Time/s
100
Atomistic
Simulation
Methods
(ms) 10-3
Mesoscale methods
Lattice Monte Carlo
Brownian Dynamics
Dissipative Particle Dynamics
(s) 10-6
(ns) 10-9
(ps) 10-12
Semi-empirical
methods
Ab initio
methods
Tight-binding
MNDO, INDO/S
(fs) 10-15
10-10
10-9
10-8
10-7
(nm)
10-6
10-5
10-4
(m)
Length/m
F.R. Hung, K.E. Gubbins, and S. Franzen, Chemical Engineering Education, Fall 2004
Monte Carlo
Ensemble average
Stochastic
No element of time
10
1.5
1.0
12 6
u(r) = 4
r
r
0.5
0.0
-0 .5
-1 .0
1.0
1.2
1.4
1.6
1.8
2.0
Separation
Intermolecular
van der Waals attraction and repulsion (Lennard-Jones form)
electrostatic
multibody
11
Theory
Experiment
test treatment
test model
Simulation
12
P = pressure (bar)
= molar density (moles/liter)
R = gas constant (0.08314 bar-liter/mol-K)
T = absolute temperature (K)
molecular model
U(r) = 0
no molecular interactions
13
p = 2 p x
1 t
P =
p
Ato t =0
o
(-px,py)
sum over long time to, or over many time origins, to get precise average
14
Approximate EOS
Percus-Yevick
virial
1 + 2 + 3 2
Pv = kT
(1 ) 2
compressibility
1+ +2
Pc = kT
(1 )3
15
Lattice models
Energy
Separation
Lessons
Attraction is needed to condense, but not to freeze
Molecular diffusion is coupled to molecular convection
No analytic equation of state can describe the critical region
Volume fraction takes the role of mole fraction in describing macromolecular
systems
Quadrupole moments raise the triple point relative to the critical point
16
Applications
Biochemical systems (1 atm, 25C)
Processes inside of zeolites
Alkane critical properties with chain length
Fits of individual properties (e.g., density, liquid enthalpy) to experiment for a few
systems
17
0.2
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Strauch and Cummings, Fluid Phase Equilibria, 86 (1993) 147-172; Chialvo and
Cummings, Molecular Simulation, 11 (1993) 163-175.
18
19
Alkane Mixtures
(Supercritical) Ethane + n-Heptane
Siepmann group
Ethane + n-heptane
10
Exp. at 366 K
TraPPE-EH at 366 K
Exp. at 450 K
TraPPE-EH at 450 K
P [MPa]
8
6
4
2
0
0
0.2
0.4
0.6
Xethane
0.8
20
Calc. 311K
100
Calc. 372 K
Expt. (Newtonian) viscosity
Predicted: 10318
(10-6 m2/s)
Viscosity
Experiment:
11630
10
0.1
Moore, 0.0001
J. D., Cui, S. T., Cummings,
P.
0.001
1
(Image of alkanes)