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School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, Shanghai 200240, China
b College of Pharmaceuticals and Biotechnology, Tianjin University, Tianjin 300072, China
Received 17 January 2005; received in revised form 15 July 2005; accepted 1 August 2005
Abstract
Widom insertion method coupled with canonical ensemble (NVT) molecular simulations based on different force fields was utilized to
calculate Henrys law constants (HLCs) of several common gas molecules, N2 , O2 , CH4 , and CO2 , in liquid ethylene oxide and ethanol.
Several simulation options, including insertion grid densities, liquid densities, force field models, and simulation methods were investigated.
The results indicate that reasonably good agreements between the calculated and experimental values were obtained using the united-atom
(UA) model. However, systematically overestimated values are obtained with the all-atom (AA) force field model. The causes of the problems
were investigated comparatively. The data indicate that hydrogen atoms in the AA model are mainly responsible for these problems, but the
underlying sampling algorithm in Widom insertions, which may be the real source of problems, needs further investigation.
2005 Elsevier B.V. All rights reserved.
Keywords: Henrys law constant; Force field; Widom insertion; Monte Carlo; Molecular dynamics simulation
1. Introduction
Henrys law constant (HLC), as a measurement of the solubility of gas molecules in solvent, is a fundamental property
in chemical engineering processes. Traditionally, HLC values are measured experimentally, which is a difficult task
especially under extreme conditions [17]. Accurate prediction using computational methods is highly desirable. Several
methods, such as QSPR [8], empirical methods based on thermodynamics principles [9], or based on solvation models of
quantum chemistry calculations [10], and molecular simulation methods [1117] have been proposed. With the advance
of computer technologies, molecular simulation methods
based on force filed technologies are regarded as promising
alternatives for predicting HLC values. In addition to the significances in applied chemistry, the calculation of the HLC
values using force field methods requires accurate evaluation
Corresponding author. Tel.: +86 21 5474 8987; fax: +86 21 5474 1297.
E-mail address: huaisun@sjtu.edu.cn (H. Sun).
0378-3812/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2005.08.008
H2,1 = lim
(1)
(2)
ij = i j
(3)
ri0 + rj0
rij0 =
.
2
The parameters, together with corresponding molecules, are
part of the TEAM force field [33].
The TEAM force field uses functional forms similar to
other AA force fields such as CFF [35], COMPASS [31],
AMBER/OPLS [29,30]. The difference however is that it
is a fragment-based force field database containing unique
fragments and associated parameters. A fragment is a complete molecule, which is either a small molecule itself (such
as H2 O, CH4 , N2 ) or a fragment cut from a large molecule
67
torsion
kba (b b0 )( 0 ) +
bondangle
i<j
0 6
12
rij0
rij
ij
2
rij
rij
where:
2( 20 )
1
c=
,d =
30 ( 0 )
20 ( 0 )
c = d = 0.0
k0 ( 0 )2
out-of-plane
bondbond
q i qj
i<j
rij
(4)
(0 = 0, )
(0 = 0, ).
68
ex,
= kT ln exp( Etest
(6)
2
where Etest is the total potential energy between the test
molecule and the solvent molecules, and can be determined
with Widom insertion method [20]; denotes the ensemble
average.
2.3. Simulation details
The liquid phase space was sampled with NVT ensemble
Monte Carlo (MC) and molecular dynamics (MD) methods. Nonbond interaction was evaluated with charge-group
based cut-off method [31] and tail corrections. The initial
liquid models were prepared by randomly packing solvent
molecules into cubic boxes with periodic boundary condition. Two hundred molecules were placed in the simulation boxes for ethylene oxide; 300 were used for the
ethanol.
2.3.1. Monte Carlo simulation
A general Metropolis Monte Carlo program was implemented. At each trial move of our program, a molecule
is randomly selected and then subject to four basic
movestranslation, rigid rotation, vibration and internal
rotation, performed in sequence. These moves are amplitudecontrolled random processes, with a criterion of about 50%
acceptance ratio. The typical maximum displacements of the
for the translation, 0.20 rad for
basic moves are ca. 0.20 A
the rigid rotation, 0.015 A for the vibration and 0.080 rad for
the internal dihedral rotation, respectively. If one of the basic
moves is rejected, the entire trial is done, and a new trail is
started. Since the molecule is selected randomly, and each
of trail moves is controlled by the Metropolis method, the
procedure meets the detailed balance condition.
We grouped 200300 success Monte Carlo trial moves
(which roughly equal the number of molecules in the simulation box) as one simulation cycle. The configuration space
was normally equilibrated for 5 104 cycles, then sampled in
an interval of 100 cycles for 105 cycles in total for computing
the HLC values.
2.3.2. Molecular dynamics simulation
The molecular dynamics (MD) simulations were carried
out using the Verlet velocity integrator [40]. The temperature
was controlled using stochastic collision method proposed by
Andrea et al. [41]. The time step was 1 fs. The models were
d (exp( Etest ))
HLC
d (exp( Etest )) .
exp( Etest )
(7)
HLC
B .
|exp( E)|
(8)
69
Table 1
Comparison of experimental, ab initio and TEAM force field calculated intramolecular properties
Molecule
Property
TEAM
B3LYP/6-311G**
Experimental [43,44]
N2
B0 (A)
(cm1 )
1.095
2358.0
1.095
2447.5
1.098
2358.0
O2
B0 (A)
(cm1 )
1.206
1580.0
1.206
1640.9
1.207
1580.0
CO2
B0 (A)
( )
1 (cm1 )
2 (cm1 )
3 (cm1 )
4 (cm1 )
1.160
180.0
2398.5
1392.6
667.0
667.0
1.160
180.0
2436.1
1375.6
666.5
666.5
1.160
180.0
2349.0
1333.0
667.0
667.0
CH4
B0 (A)
( )
1 (cm)1
2 (cm)1
3 (cm1 )
4 (cm1 )
1.091
109.5
1341.6
1561.5
3025.8
3131.9
1.090
109.5
1341.2
1561.1
3028.5
3134.8
1.094
109.5
1306.0
1534.0
2917.0
3019.0
potentials. The charge parameters were derived from ab initio electrostatic potentials. The VDW parameters were optimized using liquid densities and vaporization enthalpies of
the molecules considered, as given in Table 3. The simulated
results using the optimized force field parameters are listed
in the same table for comparison.
To further validate the force field, we applied the obtained
parameters in NPT simulations to predict the PVT equations of state for the liquids. The results are plotted in Fig. 2.
The results indicate that excellent agreements between calculation and experimental data [47] are obtained in a wide
range of temperatures.
Table 2
Comparison of experimental, ab initio, and molecular mechanics (TEAM force field) calculated geometric properties of ethanol
Molecule
Property
TEAM
B3LYP/6-311G**
Experimental [46,47]
C C (A)
C H (A)
CCH ( )
HCH ( )
HCCH ( )
1.537
1.093
111.5
107.4
122.4
1.531
1.094
111.4
107.5
122.2
1.535
1.094
111.2
Cb H3 Ca H2 OH (ethanol)
C C (A)
C O (A)
O H (A)
Ca H (A)
Cb H (A)
CCO ( )
COH ( )
Cb Ca H ( )
Ca Cb H ( )
HCa H ( )
HCb H ( )
Cb Ca OH ( )
1.532
1.429
0.963
1.096
1.095
114.1
106.7
110.1
111.7
106.7
108.4
59.9
1.525
1.425
0.962
1.100
1.093
112.7
107.7
110.2
111.0
107.2
107.6
61.5
1.530
1.425
0.945
1.094
1.094
107.3
108.5
110.3
109.1
108.6
C C (A)
C O (A)
C H (A)
HCH ( )
HCHC ( )
1.468
1.430
1.087
115.499
26.249
1.468
1.429
1.087
115.382
26.184
1.466
1.431
1.085
116.600
22.000
(ethylene oxide)
70
Table 3
Experimental data and NVT MD simulation results for the liquid models
Liquid model
Nitrogen
Nitrogen (UAa )
Oxygen
Oxygen (UA)
Carbon dioxide
Methane
Ethane
Ethanol
Ethylene oxide
a
Experimental [47]
Calculated
(g/cm3 )
T (K)
77.35
77.35
90.17
90.17
216.60
111.66
184.55
320.00
298.20
0.8078
0.8078
1.1420
1.1420
1.1790
0.4240
0.5447
0.7665
0.8624
Hvap (kcal/mol)
Hvap (kcal/mol)
1.3571
1.3571
1.6104
1.6104
3.6500
1.9497
3.5083
9.5414
5.9537
1.3557
1.3510
1.6111
1.6070
3.6549
1.9473
3.5044
9.5431
5.9518
0.1023
0.4495
0.04347
0.2111
0.1343
0.1231
0.1112
0.01782
0.06957
UA = united-atom force field. Except the molecules denoted as UA, the other molecules were all simulated with TEAM all-atom force field.
71
listed for comparison. Using the TEAM force field, the predictions are generally overestimated; especially for CH4 , the
calculated values are about three times larger than the experimental data. We performed the calculations with UA model
(TraPPE), the results are in much better agreements with the
Fig. 2. Comparisons of calculated () and experimental (solid line) densities under saturated pressure. (a) Nitrogen; (b) nitrogen (UA); (c) oxygen; (d) oxygen
(UA); (e) carbon dioxide; (f) methane; (g) ethane; (h) ethanol; (i) ethylene oxide. Note: UA = united-atom force field. Except the molecules denoted as UA, the
other molecules were all simulated with TEAM all-atom force field.
72
Fig. 2. (Continued).
Table 4
Henrys law constant (in MPa) calculated for argon in liquid ethylene oxide
T (K)
273.15
Da [47] (g/cm3 )
Gridb
MDc
0.8974
103
MCd
0.061
0.491
1.656
3.926
7.668
125.5
123.2
125.3
125.0
124.8
21.3
7.4
10.1
10.2
10.5
117.3
145.1
147.8
148.1
148.0
40.5
21.5
20.8
19.7
19.6
167.0
203
303
403
503
Experimental [48]
298.15
0.8624
103
203
303
403
503
0.059
0.472
1.592
3.773
7.369
131.9
133.4
131.9
132.3
132.3
6.9
5.1
5.6
5.7
5.7
132.0
133.6
134.7
135.1
135.1
8.1
21.8
18.9
19.2
19.0
142.0
323.15
0.8252
103
203
303
403
503
0.056
0.451
1.523
3.610
7.051
125.8
128.7
127.8
128.2
128.2
3.4
3.2
3.2
2.7
1.7
141.4
135.4
134.9
135.0
135.0
9.9
10.5
10.3
10.5
10.6
127.0
a
b
c
d
73
Table 5
Henrys law constant (in MPa) of N2 /CH4 /C2 H6 in ethylene oxide
Methoda
Potential modelb
Temperature (K) of
273.15
298.15
323.15
(a) N2
MD
MC
MD
MC
Experimental HLC [48]
AA/AA
AA/AA
AA/UA
AA/UA
249.6 21.4
344.7 47.5
162.2 15.3
208.5 44.2
280
256.6 14.9
247.3 50.7
174.1 10.1
174.2 36.3
218
224.5 6.4
230.2 31.5
159.8 6.1
169.5 18.1
182
(b) CH4
MD
MC
MD
MC
Experimental HLC [48]
AA/AA
AA/AA
AA/UA
AA/UA
124.0 19.1
178.9 82.1
36.6 4.8
49.7 12.0
61.3
150.4 12.4
147.1 31.0
50.0 3.5
48.6 12.6
61.4
144.3 6.6
148.8 18.4
53.4 2.4
55.6 6.9
59.5
(c) C2 H6
MD
MC
MD
MC
Experimental HLC [48]
AA/AA
AA/AA
AA/UA
AA/UA
17.0 10.8
17.1 30.5
5.7 2.4
6.6 6.3
8.4
34.7 10.7
15.8 5.9
11.3 3.0
7.9 4.2
10.9
33.6 8.1
34.0 12.2
11.0 1.4
9.9 4.3
12.9
a
b
experimental data. The MD and MC generated configurations yield similar results, certainly within the uncertainties,
as given in the table.
3.3. Prediction of HLC of N2 , O2 , CO2 , and CH4 in
liquid ethanol
The calculated HLC values of N2 , O2 , CH4 and CO2 in
liquid ethanol at two specific temperatures are compiled in
Table 7, together with the experimental data [49] published
by the IFPSC committee for comparison. It is well known
that the liquid density has strong impact on the calculated
HLC, hence we carried out the calculations using four liquid
densitiesthe experimental densities, the GEMC simulated
densities [38] using the UA model, the NPT MD simulated
densities using the UA model, and NPT MD simulated densities using the AA model. The densities are summarized in
Table 6. The density models used in the prediction are listed
in the first column of Table 7. The second column lists the
simulation methods used for generating the configurations of
Table 6
Calculated and experimental densities (in g/cm3 ) of liquid ethanol
Temperature (K)
GEMC [38]
TraPPE
TEAM
Experimental [47]
275
300
323
325
373
375
425
475
0.804
0.782
0.754
0.756
0.704
0.705
0.635
0.524
0.800
0.780
0.764
0.761
0.715
0.703
0.647
0.552
0.813
0.789
0.772
0.769
0.728
0.725
0.676
0.628
0.808
0.786
0.764
0.762
0.710
0.708
0.643
0.553
74
Table 7
Henry law constants (in MPa) of N2 , O2 , CH4 and CO2 gas molecules in ethanol at 323 and 373 K
Densitya
Potential (ethanol/gas)c
N2
(a) 323 K
Expt.
MD
Expt.
MD
Expt.
MD
Expt.
MD
Expt.
MC
Expt.
MC
GEMC
MD
GEMC
MD
GEMC
MC
GEMC
MC
NPT
MD
NPT
MD
Experimental HLC (MPa)[48]
AA/AA
AA/UA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
980.0
618.2
223.8
236.7
232.5
260.3
213.4
233.8
200.9
221.7
194.6
217.9
253.6
441.6
250.2
26.3
31.0
10.3
11.0
19.2
32.5
9.1
11.3
9.3
11.7
7.6
396.5
253.4
132.5
140.4
136.9
152.9
123.5
135.1
120.0
132.2
121.9
135.3
174.8
137.0
73.4
12.5
16.5
5.0
4.5
6.2
13.1
3.4
4.3
4.7
6.2
8.7
545.7
179.5
100.6
128.9
104.9
135.0
97.5
122.8
91.3
117.7
85.0
105.3
81.5
187.7
80.2
14.1
8.9
4.4
4.2
10.7
12.4
5.0
6.6
6.2
10.5
2.4
69.8
73.4
50.9
29.3
58.7
29.2
54.2
27.7
44.7
30.4
35.8
22.0
21.1
80.5
122.7
9.4
6.7
5.7
4.4
10.3
10.6
4.9
2.5
10.0
6.8
1.1
(b) 373 K
Expt.
MD
Expt.
MD
Expt.
MD
Expt.
MD
Expt.
MC
Expt.
MC
GEMC
MD
GEMC
MD
GEMC
MC
GEMC
MC
NPT
MD
NPT
MD
Experimental HLC (MPa) [48]
AA/AA
AA/UA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
UA/UA
UA/AA
460.6
327.7
207.2
221.8
200.7
218.6
189.1
204.2
188.5
206.7
218.9
235.8
221.3
58.7
28.9
14.7
13.7
7.6
7.0
7.6
10.6
6.3
6.2
16.5
18.4
13.3
252.2
177.0
135.7
145.8
133.4
145.2
126.7
136.9
126.0
138.4
142.7
153.5
159.9
23.3
9.8
6.9
6.4
3.8
3.5
4.7
7.1
2.7
2.8
8.5
9.6
12.8
283.7
117.9
111.1
143.9
106.7
135.7
100.3
124.8
100.9
127.4
116.1
145.7
83.4
15.1
13.3
9.0
12.2
4.7
5.7
4.9
6.2
3.7
4.8
9.6
10.9
5.0
31.3
45.2
66.1
36.6
63.6
37.0
57.7
29.6
59.1
34.8
67.2
40.1
29.7
15.9
15.8
8.4
6.9
4.8
5.0
3.6
9.8
1.9
3.2
12.2
8.0
3.3
a
b
c
Methodb
O2
CH4
CO2
A comparison of Table 7a with Table 7b shows the temperature dependence of the calculated HLC values. To further
explore the temperature dependence of the calculated HLC
values, we extended the calculations using the most successful model (UA/AA force fields, experimental densities, and
MD simulated configurations) over a temperature range of
275475 K. The results are presented in Fig. 3. It is clearly
that each of the predicted HLC curves has a maximum, which
qualitatively agree with existing HLC experimental data
[50].
In order to find out the causes of the large errors in calculated HLC using the AA force field model, we analyzed
the temperature dependence of data calculated using the AA
force field model. As given in Table 7, when the temperature
changes from 373 to 323 K, the calculated HLC values for
N2 increases about 520 MPa. In comparison, the calculated
values (ca. 145 MPa) of O2 are significantly smaller. Both
molecules are non-polar, linear; the simulation conditions
were the same except the force field parameters. Close examination of the force field parameters as given in the supplementary material of this article indicates that the Lennard-Jones
= 0.0738 kcal/mol)
(LJ) parameters for N2 (r0 = 3.6989 A,
Fig. 3. Henrys law constants of N2 , O2 , CH4 and CO2 in ethanol with experimental density. Hollow points and the solid lines represent the calculated
HLC with Widom method. Solid points are the experimental HLC values.
( , ) N2 ; (, ) O2 ; (,
) CH4 ; (, ) CO2 .
75
Table 8
HLC values of a hypothetic diatomic molecule in ethanol
No.
1
2
3
4
5
6
7
a
Lennard-Jones parameters
r0 (A)
(kcal/mol)
323 K
3.8
3.7
3.6
3.6
3.6
3.6
3.6
0.0734
0.0734
0.0734
0.0634
0.0838
0.0938
0.1000
570.1
513.1
461.3
690.8
309.7
214.9
172.6
373 K
67.3
53.8
42.2
61.7
29.0
20.5
16.7
288.3
268.4
249.9
342.5
183.9
137.5
115.8
13.9
11.2
9.0
12.1
7.1
5.1
4.3
281.8
244.7
211.4
348.3
125.8
77.4
56.8
Table 9
Henrys law constants (in MPa) of argon and helium in liquid ethanol
Temperature (K)
Argon
323
373
323
373
0.7635
0.7103
0.7635
0.7103
AA
AA
UA
UA
323.3
203.7
147.8
148.0
Helium
17.3
12.9
14.3
7.9
1614.0
856.1
455.3
346.2
79.2
29.9
8.2
5.3
4. Conclusion
We have investigated the feasibility of using all-atom (AA)
force field model with Widom insertion method to predict
Henrys Law Constant in this project. Using ab initio and
liquid data, we developed a set of TEAM force field parameters, and validated these parameters by calculating molecular
structures, vibrational frequencies, heats of vaporization and
PVT equations of states of liquids. The agreements with
experimental data are generally satisfactory. We then studied several options in the calculations of HLC values. We
utilized a grid-based insertion scheme, optimized the den 3 was
sity of the grid points. A minimum value of 0.5 grids/A
found to be required for the accuracy and convergence of the
HLC calculation results. We implemented a simple MC simulation engine, and compared the configuration space made
by the MC simulations with that made by MD simulations;
the results are in close agreement. By comparing our calculation results with the experimental data and calculated
data in the literature [42], we validated our Widom insertion
code.
Our main problem however remains unsolved yet. Using
the AA force field model, the calculated HLC values are systematically overestimated. We have investigated this problem
by comparing different molecular systems and different force
field models. Especially, we focus on the temperature dependence of the calculated HLC values using different models.
The obtained results are consistent so that we can make the
following statements based on our observations.
(1) The problem becomes more serious at low temperature
when the density of solvent is large.
76
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