Liquid water MD simulation

A lot of stories on water:

Please refer to the excellent web-site

Martin Chaplin’s “Water Structure and Science”
http://www.lsbu.ac.uk/water/index2.html
 ε / kJ
Model Type σ/Å l1 Å l2 Å q1 (e) q2 (e) θ° φ°
mol-1

+0.423 -0.847
SPC/E a 3.166 0.650 1.0000 - 109.47 -
8 6

3.1506 +0.417 -0.834

TIP3P a 0.6364 0.9572 - 104.52 -
1 0 0

3.1536 +0.520 -1.040

TIP4P c 0.6480 0.9572 0.15 104.52 52.26
5 0 0

TIP4P- 3.1643 0.6809 +0.524 -1.048

c 0.9572 0.125 104.52 52.26
Ew 5 46 22 44

TIP5P- +0.241 -0.241 109.4

d 3.097 0.7448 0.9572 0.70 104.52
Ew 0 0 7 Water model potential

SPC/E: H. J. C. Berendsen, J. R. Grigera and T. P. Straatsma, The missing term in effective pair potentials, J. Phys. Chem. 91 (1987) 6269-6271.
TIP3P: W. L. Jorgensen, J. Chandrasekhar, J. D. Madura, R. W. Impey, and M. L. Klein, Comparison of simple potential functions for simulating liquid water, J.
Chem. Phys. 79 (1983) 926-935
TIP4P: W. L. Jorgensen and J. D. Madura, Temperature and size dependence for monte carlo simulations of TIP4P water, Mol. Phys. 56 (1985) 1381-1392.
TIP4P-Ew: H. W. Horn, W. C. Swope, J. W. Pitera, J. D. Madura, T. J. Dick, G. L. Hura and T. Head-Gordon, Development of an improved four-site water model
for biomolecular simulations: TIP4P-Ew, J. Chem. Phys. 120 (2004) 9665-9678.
TIP5P-Ew: S. W. Rick, A reoptimization of the five-site water potential (TIP5P) for use with Ewald sums, J. Chem. Phys. 120 (2004) 6085-6093.
TIP5P: M. W. Mahoney and W. L. Jorgensen, A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential
functions, J. Chem. Phys. 112 (2000) 8910-8922.
 Calculated results：classical MD
Average
Density Expansion
Dipole Dielectric Self diffusion, configurational
Model maximum, coefficient,
moment constant 10-5 cm2/s energy, kJ
°C 10-4 °C-1
mol-1

Exp. 2.95 78.4 2.30 -41.5 +3.984 2.53

SPC/E 2.35 71 2.49 -41.5 -38 5.14

TIP3P 2.35 82 5.19 -41.1 -91 9.2

TIP4P 2.18 53 3.29 -41.8 -25 4.4

TIP4P-Ew 2.32 62.9 2.4 -46.5 +1 3.1

TIP5P-Ew 2.29 92 2.8 - +8 4.9

All the data is at 25°C and 1 atm

==>The popular models SPC, SPC/E, TIP3P and TIP4P produce poor agreement with water's
melting point (giving melting points of 190 K, 215 K, 146 K and 232 K respectively)

==>The popular TIP4P model underestimates the tetrahedrality of the water molecule's
environment, which explains its poor estimate of the dielectric constant. It is, however, remarkably
good at qualitatively describing water's phase diagram. The SPC/E and TIP4P models are reported as
failing to properly describe the experimental O···O radial distribution function. The TIP3P and SPC
show particularly poor agreement, the TIP4P, SPC/E and PPC show improved agreement.
 model
potential
SCORE ==> We will use
SPC/E
and
TIP4P/Ew
models.

flexible model: time consuming and not improved from rigid model
Polarizable model: so far not significantly improved, but maybe important for
ion solvation, for interface, and for ILs
 ALS2000 and Soper 2000

ALS:X-ray 2000
Narten: X-ray 1972
Soper: Neutron 97
Soper 2000:reanalysis of
1997 data

good agreement !!
SPC/E and ALS2000

Radial distribution
function(RDF)
from exp.
and MD.
 first-pinciples
MD is getting
Classical model better.
potentials can
explain
the Exp. results
very well.

Exp. results are

also improving.

Radial distribution
function from exp.
and MD.
Here we use one of the water model SPC/E or TIP4P-Ew

1) L-J interaction is oxygen-oxygen only.

2) rigid molecule is assumed. ==> Cal. become faster
O-H distance is const.
angle H-O-H is const.
==> Cal. become faster
==> but neglect the vibrational degree of freedom.
==> we should select how we impose the constraints on
bond length and bond angle.

3) no electrostatic interaction between the intramolecular

atoms.
 Z X

initial configuration: ice?

Cubic Ice

fcc + half the tetrahedral sites are filled.

ρ / g cm-3 = 0.996516
H2O all site(fcc+t-site)= 512
liquid water all atom number= 1536
ax,ay,az,volume= 24.86, 24.86, 24.86 Å 15370.0
 Z

SPC/E model

-0.8476 e

1.0000 Å

109.47°
+0.4238 e

r(OH)=1.0000 Å
θ(HOH)=109.47 intermolecular interaction
are fixed. z(O)=-0.8476 e
z(H)=0.4238 e
ε(O) = 0.650 kJ mol-1
σ(O) = 3.166 Å
 CONFIG
H2O liquid SPCE water at 300 K
FIELD
2 1
24.8632886676 .0000000000 .0000000000 H2O SPC/E
.0000000000 24.8632886676 .0000000000 units kJ
.0000000000 .0000000000 24.8632886676 molecules 1
OW 1
-12.4316443338 -12.4316443338 -12.4316443338 SPCE water
-.1157118156 -.1006883860 .0252069353 nummols 512
.0000000000 .0000000000 .0000000000 atoms 3
HW 2
-11.8542984133 -11.8542984133 -11.8542853673
OW 15.9996 -0.8476
-.1157118156 -.1006883860 .0252069353 HW 1.0008 0.4238
.0000000000 .0000000000 .0000000000 HW 1.0008 0.4238
HW 3
constraints 3
-13.0089902543 -13.0089902543 -11.8542853673
-.1157118156 -.1006883860 .0252069353 1 2 1.0000
.0000000000 .0000000000 .0000000000 1 3 1.0000
OW 4 2 3 1.63298
-10.8776887921 -10.8776887921 -10.8776887921
-.0944489040 .0834090526 -.0070384049 finish
.0000000000 .0000000000 .0000000000 vdW 3
HW 5 OW OW lj 0.6507346 3.165492
-10.3003428716 -11.4550347126 -10.3003298256
-.0944489040 .0834090526 -.0070384049 OW HW lj 0.0 3.165492
.0000000000 .0000000000 .0000000000 HW HW lj 0.0 0.0
HW 6 close
-11.4550347126 -10.3003428716 -10.3003298256
-.0944489040 .0834090526 -.0070384049
.0000000000 .0000000000 .0000000000
...
OW 1534
7.7697777086 10.8776887921 10.8776887921
.0179460404 .0359122702 .0141856681
.0000000000 .0000000000 .0000000000
HW 1535
8.3471236291 10.3003428716 11.4550477586
.0179460404 .0359122702 .0141856681
.0000000000 .0000000000 .0000000000
HW 1536
7.1924317881 11.4550347126 11.4550477586
.0179460404
.0000000000
.0359122702
.0000000000
.0141856681
.0000000000
SPC/E model
CONTROL NVE CONTROL NPT 300 K 1 atom
SPC/E model of water
SPC/E model of water
integrator velocity verlet
integrator velocity verlet temperature 300.00
temperature 300.00 ensemble npt hoover 0.1 0.2
ensemble nve
steps 150000
steps 150000 equilibration 100000
equilibration 100000
multiple step 1
multiple step 1
scale 10
scale 10
print 50 print 50
stack 100 stack 100
stats 10 stats 10
rdf 1 rdf 1
traj 1 100 0 traj 1 100 0

timestep 0.001 timestep 0.001

cutoff 9.50 cutoff 9.50
delr width 0.5000 delr width 0.5000
ewald precision 1d-6 ewald precision 1d-6
shake tolerance 1.0E-5 shake tolerance 1.0E-5
quaternion tolerance 1.0E-5 quaternion tolerance 1.0E-5
print rdf print rdf
pres 0.001
job time 150000.00
close time 500.00
job time 150000.00
finish close time 500.00

finish

SPC/E model
NVE : microcanonical ensemble 
==> total energy conserved
==> directly linked to mechanics
==> kBT = kinetic energy
Temperature fluctuates
but the termal average should be the same
NVT : canonical ensemble
==> T keeps constant and
the heat exchange (or momentum exchange)
with the virtual reservoir (thermostat)
===> some tricks are needed.
Nose-Hoover algorithm is only well defined!!

Text

NVT
NPT ensemble
==> T and P keeps constant and
the heat exchange and cell size change
dynamically.
===> Hoover barostat method is only well defined!!

Text
Pext

NPT
 SPC/E model:
time elapsed since job start = 27144.723 seconds
NVE ensemble
results
temp 2.9618E+02 K r.m.s. fluctuation 6.3217E+00 K
3.0
SPC/E model of liquid water: NVE ensemble
Approximate 3D Diffusion coefficients (10^-9 m^2 / s)

atom D 2.5
OW 2.6341E+00 g(O-O)
HW 2.6341E+00 g(O-H)
g(H-H)

radial distribution function

2.0

Average pressure tensor

-8.2421E-02 2.9661E-02 5.1028E-03
2.9661E-02 -3.2231E-02 2.5959E-02 1.5
5.1028E-03 2.5959E-02 -8.3213E-02

trace/3. -6.5955E-02 katom 1.0

0.5

0.0
2 4 6 8
distance / Angstrom
SPC/E model:
NPT ensemble
results
T = 3.0011E+02 K r.m.s. fluc. 7.1254E+00 K

Approximate 3D Diffusion coefficients (10^-9

m^2 / s)

atom D
OW 2.4579E+00
HW 2.4818E+00
movie
Average pressure 1.2925E-03 katom
Average pressure tensor r.m.s. fluctuations
-3.3618E-02 1.3665E-02 3.6790E-02 6.2210E-01 5.0643E-01 5.1488E-01
1.3665E-02 -1.0684E-02 5.6640E-03 5.0643E-01 6.1777E-01 5.0854E-01
3.6790E-02 5.6640E-03 4.8179E-02 5.1488E-01 5.0854E-01 6.2829E-01
trace/3. 1.2925E-03

Average cell vectors r.m.s. fluctuations

24.8372539181 .0000000000 .0000000000 7.1583E-02 0.0000E+00 0.0000E+00
.0000000000 24.8372539181 .0000000000 0.0000E+00 7.1583E-02 0.0000E+00
.0000000000 .0000000000 24.8372539181 0.0000E+00 0.0000E+00 7.1583E-02

time elapsed since job start = 24121.500 seconds

SPC/E model:
cf. exp. results
NPT ensemble
results
3.0

2.5
SPC/E liquid water NPT ensemble
g( O-O )
g (O-H )
g( H-H )
2.0
radial distribution function

1.5

1.0

0.5

0.0
2 4 6 8
distance / Angstrom
TIP4P/Ew model r(OH)=0.9572 Å z(M)=-1.04844 e
r(OM)=0.125 Å z(H)=0.52422 e
O θ(HOH)=104.52 ε(O) = 0.680946 kJ mol-1
θ(MOH)=52.26
Active
σ(O) = 3.16435 Å Y

are fixed.
Z X

mass of M is zero.
M
H H

M: dummy charge site

 CONFIG FIELD
TIP4P H2O liquid water 300 K
2 1 H2O TIP4P
24.8632889271 .0000000000 .0000000000 units kJ
.0000000000 24.8632889271 .0000000000 molecules 1
.0000000000 .0000000000 24.8632889271
OW 1 TIP4P water
-12.4316444636 -12.4316444636 -12.4316444636 nummols 512
-.1157118180 -.1006883881 .0252069358 atoms 4
.0000000000 .0000000000 .0000000000 OW 15.9996 0.0
HW 2 HW 1.0008 0.52422
-11.8963997541 -11.8963997541 -11.8457621869 HW 1.0008 0.52422
-.1157118180 -.1006883881 .0252069358 MW 0.0 -1.04844
.0000000000 .0000000000 .0000000000
HW 3 constraints 3
-12.9668891730 -12.9668891730 -11.8457621869 1 2 0.95720000
-.1157118180 -.1006883881 .0252069358 1 3 0.95720000
.0000000000 .0000000000 .0000000000 2 3 1.51390065
MW 4 rigid 1
-12.4316444636 -12.4316444636 -12.3066444636 2 1 4
-.1157118180 -.1006883881 .0252069358 finish
.0000000000 .0000000000 .0000000000
OW 5 vdW 6
-10.8776889056 -10.8776889056 -10.8776889056 OW OW lj 0.680946 3.16435
-.0944489059 .0834090543 -.0070384050 OW HW lj 0.0 0.0
.0000000000 .0000000000 .0000000000 HW HW lj 0.0 0.0
HW 6 OW MW lj 0.0 0.0
-10.3424441962 -11.4129336150 -10.2918066290 HW MW lj 0.0 0.0
-.0944489059 .0834090543 -.0070384050 MW MW lj 0.0 0.0
.0000000000 .0000000000 .0000000000
HW 7 close
-11.4129336150 -10.3424441962 -10.2918066290
-.0944489059 .0834090543 -.0070384050
.0000000000 .0000000000 .0000000000
MW 8
-10.8776889056 -10.8776889056 -10.7526889056
-.0944489059 .0834090543 -.0070384050
.0000000000 .0000000000 .0000000000
CONTROL NVE CONTROL NPT 300 K 1 atom
TIP4P model of water TIP4P model of water

integrator velocity verlet integrator velocity verlet

temperature 300.00 temperature 300.00
ensemble nve ensemble npt hoover 0.1 0.2

steps 150000
steps 150000
equilibration 100000
equilibration 100000 multiple step 1
multiple step 1 scale 10
scale 10 print 50
print 50 stack 100
stack 100 stats 10
stats 10 rdf 1
rdf 1 traj 1 100 0
traj 1 100 0
timestep 0.001
timestep 0.001 cutoff 9.50
cutoff 9.50 delr width 0.5000
delr width 0.5000 ewald precision 1d-6
ewald precision 1d-6 shake tolerance 1.0E-5
shake tolerance 1.0E-5 quaternion tolerance 1.0E-5
print rdf
quaternion tolerance 1.0E-5
pres 0.001
print rdf
job time 300000.00
job time 300000.00 close time 500.00
close time 500.00
finish
finish
 TIP4P/Ew model: NVE ensemble results movie
temp_tot 3.0270E+02 K r.m.s. fluctn. 6.4702E+00 K

Approximate 3D Diffusion coefficients (10^-9 m^2 / s)

atom D
OW 2.6537E+00
HW 2.6627E+00
MW 2.6538E+00

Average pressure tensor r.m.s. fluctuations

4.8443E-02 6.8694E-03 1.4413E-02 7.6492E-01 5.0866E-01 5.1297E-01

6.8694E-03 3.8647E-02 2.9359E-02 5.0866E-01 7.9529E-01 5.0658E-01
1.4413E-02 2.9359E-02 4.2101E-02 5.1297E-01 5.0658E-01 8.0716E-01

trace/3. 4.3064E-02
3.0
TIP4P/Ew NVE ensemble
g(O-O)
2.5 g(O-H)
g(H-H)
2.0
RDF

1.5

1.0

0.5

0.0
2 4 6 8
distance / Angstrom

time elapsed since job start = 34789.530 seconds

 TIP4P/Ew model: NPT ensemble results
Temp. 2.9996E+02 K +- 7.7193E+00

Approximate 3D Diffusion coefficients

(10^-9 m^2 / s)

atom
OW
D
2.5677E+00
movie
HW 2.5421E+00
MW 2.5601E+00
Average pressure tensor r.m.s. fluctuations

2.3043E-02 -3.2620E-02 1.5465E-02 8.9626E-01 5.0277E-01 4.8920E-01

-3.2620E-02 4.4084E-03 -1.0378E-02 5.0277E-01 8.5233E-01 4.9858E-01
1.5465E-02 -1.0378E-02 -1.3775E-02 4.8920E-01 4.9858E-01 8.6417E-01

trace/3. 4.5587E-03

Average pressure
4.5587E-03 katom

Average cell vectors r.m.s. fluctuations

24.8869811588 .0000000000 .0000000000 1.0249E-01 0.0000E+00 0.0000E+00

.0000000000 24.8869811588 .0000000000 0.0000E+00 1.0249E-01 0.0000E+00
.0000000000 .0000000000 24.8869811588 0.0000E+00 0.0000E+00 1.0249E-01

time elapsed since job start = 34773.057 seconds

TIP4P/Ew model: NPT ensemble results

cf. exp. results

3.0

2.5
TIP4PEw NPT ensemble
g(O-O)
2.0 g(O-H)
g(H-H)
 RDF

1.5

1.0

0.5

0.0
2 4 6 8
distance / Angstrom