LAMMPS - Molecular Insight into the Lower Critical Solution … · 2019-09-09 · Hyungmook...
Transcript of LAMMPS - Molecular Insight into the Lower Critical Solution … · 2019-09-09 · Hyungmook...
Hyungmook Kang,1,2 David E. Suich,3 Robert Kostecki,3 Jeffrey J. Urban 1,*
1 The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA2 Department of Mechanical Engineering, University of California, Berkeley, CA
3 Energy Storage and Distributed Resources Division, Lawrence Berkeley National Laboratory, Berkeley, CA
Molecular Insight into the Lower Critical Solution Temperature Transition of Ionic Liquids
2019 LAMMPS Workshop and Symposium August 15, Albuquerque NM
Introduction
Te
mp
era
ture
composition
1 phase
2 phases
LCST
2 phases
UCST
Visualization
50 wt.% [P4444][DMBS]
LCST behaviorA thermo-responsive spontaneous phase-separation behavior
At temperatures below LCST, the system is completely miscible in all proportions, whereas above LCST partial liquid miscibility occurs.
with the critical temperature, called the Lower Critical Solution Temperature
Forward Osmosis desalination process based on Ionic Liquids with LCST behavior
Feed DrawH2O
NFFO
solar or waste heat
draw agent regeneration
water with small molecule IL
sea water of brackish waterpurified water
draw agentrecycling
H2O
H2O
H2O
Nile Red dye dissolved by IL
39 oC35 oC
T ↑
Particle size by Dynamic Light Scattering (DLS)50 wt.% [P4444][DMBS]
Scientific QuestionsHow does the molecular environment depend on temperatureand LCST phase transition ?
Why can a minor chemical change induce markedly different phenomena ?
[P4444][DMBS] [P4444][BnzSO3]
with LCST behavior without LCST behavior
1.
2.
At above Tc range, a stronger attractive interaction
was observed between the cations and anions.
Radial Distribution Functions between P cation – S anion
The mostly charged atom represents the position of each ion. i.e. P atoms for the cations, S atoms for the anions
The more thermal motion at higher temperature
0 5 10 150
1
2
3
4
0 5 10 150
0.5
1
1.5
g(r)
r (A)o
anion-anion
0 5 10 150
0.5
1
1.5
2
g(r)
r (A)o
cation-cation
0 5 10 150
1
2
3
4
cation-anion
g(r)
r (A)o
2 4 6 80
1
2
3
water-anion
g(r)
r (A)o
0 5 10 150
0.2
0.4
0.6
0.8
1
1.2
water-cation
g(r)
r (A)o
2 4 6 801234567
water-water
g(r)
r (A)o
a)
b)
c)
d)
e)
f)
T = 20 Co
50 Co
P+
Bu
Bu Bu
Bu
SO3-
0 5 10 150
1
2
3
4
g(r
)
r (Å)
Typical trend
P S
0 5 10 150
1
2
3
0 5 10 150
1
2
3
0 5 10 150
1
2
3
0 5 10 150
1
2
3
0 5 10 150
1
2
3
4
5
cation-anion
g(r)
r (A)o
0 5 10 150
0.5
1
1.5
2
g(r)
r (A)o
0 5 10 150
1
2
3
g(r)
r (A)o
cation-cation
anion-anion
0 5 10 150
0.20.40.60.81
1.2
water-cation
g(r)
2 4 6 80
2
4
6
water-water
g(r)
r (A)o
2 4 6 80
0.5
1
1.5
2
2.5
water-anion
g(r)
r (A)o
r (A)o
a)
b)
c)
d)
e)
f)
T = 10 Co
20 Co
60 Co50 Co
r (Å)
g(r
)
P S
Counter-intuitive
0 5 10 150
0.5
1
1.5
2
the peaks between 5 and 12 Å can be interpreted as all located in the first coordination shell.
between P cation – P cation
g(r
)
r (Å)
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1
2
3
4
5
cation-anion
g(r)
r (A)o
0 5 10 150
0.5
1
1.5
2
g(r)
r (A)o
0 5 10 150
1
2
3
g(r)
r (A)o
cation-cation
anion-anion
0 5 10 150
0.20.40.60.81
1.2
water-cation
g(r)
2 4 6 80
2
4
6
water-water
g(r)
r (A)o
2 4 6 80
0.5
1
1.5
2
2.5
water-anion
g(r)
r (A)o
r (A)o
a)
b)
c)
d)
e)
f)
T = 10 Co
20 Co
60 Co50 Co
[P4444][DMBS] with LCST behavior
~ 6 Å
[P4444]+
Since the RDF is averaged data, the multiple peaks come from different orientations so thus mean the ions are loosely tied.
The peaks are merged at elevated temperatures and a major peak is observed at above Tc range.
- The ions are compactly tied to each other by the strong electrostatic forces
- The ion-pair aggregation is in the dense form of multiple layers of cation-anion shells.
Evidence of clustering at above Tc range
but, what drives this phenomena?
P+
P+
Considering the size of the single cation with even C4H9 group,
P P
Counting Hydrogen bonds in MD simulation
2
( )( )4n
dn rg rr drr p
= !"#$%&'(&) = +,
-./0423-4 3 5"63
g(r
)
RDF between O and H in water
H-bonds< r = 2.45 A
r[A] r[A]
g(r
)
RDF between O in anions and H in water
H-bonds< r = 2.45 A
(The first coordination shell)
Target Application
Motivation
LAMMPS set up
Validation of MD results
39 oC35 oC
Draw Agents: Ionic Liquids with LCST behaviorcation
tetrabutylphosphonium
[P4444]+
anion
4-toluenesulfonate
[ToS]-
2,4-dimethylbenzenesulfonate4-vinylbenzenesulfonate
[VBS]- [DMBS]-
0
1
2
3
4
5
6
Dra
wn
wa
ter
in 1
h (
g)
[VBS] [ToS] [DMBS]
Common
[P4444]+ cation
FO performance using 10 wt.% ILs as draw solutions
Best
candidate
More water molecules participate in perfecting the hydration shell of ILs
(there is essentially no free water for solutions > 50 wt.%)
The gain or loss of the directional bonding
has been used to explain the behavior of small molecules
[G.D. Smith et. al., Phys Rev Lett, 2000]
HydrationHydrogen bonds
or
Water molecules in these systemsessentially contribute to Main H-bonds in these systems
H
0 5 10 150
0.5
1
1.5
g(r)
r (A)o
anion-anion
0 5 10 150
0.5
1
1.5
2
g(r)
r (A)o
cation-cation
0 5 10 150
1
2
3
4
cation-anion
g(r)
r (A)o
2 4 6 80
1
2
3
water-anion
g(r)
r (A)o
0 5 10 150
0.2
0.4
0.6
0.8
1
1.2
water-cation
g(r)
r (A)o
2 4 6 801234567
water-water
g(r)
r (A)o
a)
b)
c)
d)
e)
f)
T = 20 Co
50 Co
P+
Bu
Bu Bu
Bu
SO3-
Common cation
[P4444]+
The hydration shell of ILs is the necessary requirement for the LCST
25 30 35 40100
101
102
103
104
25 30 35 40 45 50 550
1002003004005006007008009001000
a
b Temperature ( C)o
Temperature ( C)o
Par
ticle
siz
e (n
m)
Par
ticle
siz
e (n
m)
Miscible phaseAqueous phaseIonic liquid phase
SO3- P+
Bu
BuBu
Bu
SO3- P
+Bu
BuBu
Bu
Tc
25 30 35 40100
101
102
103
104
25 30 35 40 45 50 550
1002003004005006007008009001000
a
b Temperature ( C)o
Temperature ( C)o
Par
ticle
siz
e (n
m)
Par
ticle
siz
e (n
m)
Miscible phaseAqueous phaseIonic liquid phase
SO3- P+
Bu
BuBu
Bu
SO3- P
+Bu
BuBu
Bu
Tc
50 wt.% [P4444][BnzSO3]vs.
Discussion
Work at the Molecular Foundry was supported by the Office ofScience, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
Acknowledgement
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1.2
1.4
1.6
1.8
2
2.2
2.4
0 10 20 30 40 50 60 701
1.2
1.4
1.6
1.8
2
2.2
2.4
Temperature ( C)o
Num
ber o
f H-b
onds
per
O a
tom O -H A W
O -H W W*SO3
-
[BnzSO3]
SO3-
[DMBS]
without LCST behavior
0 10 20 30 40 50 60 701
1.2
1.4
1.6
1.8
2
2.2
2.4
T ( C)o
Num
ber o
f H-b
onds
O -H A W
O -H W W*
0 10 20 30 40 50 60 701
1.2
1.4
1.6
1.8
2
2.2
2.4
Temperature ( C)o
Num
ber o
f H-b
onds
per
O a
tom O -H A W
O -H W W*SO3
-
[BnzSO3]
SO3-
[DMBS]
0 10 20 30 40 50 60 701
1.2
1.4
1.6
1.8
2
2.2
2.4
Temperature ( C)o
Num
ber o
f H-b
onds
per
O a
tom O -H A W
O -H W W*SO3
-
[BnzSO3]
SO3-
[DMBS]
0 10 20 30 40 50 60 701
1.2
1.4
1.6
1.8
2
2.2
2.4
Temperature ( C)o
Num
ber o
f H-b
onds
per
O a
tom O -H A W
O -H W W*SO3
-
[BnzSO3]
SO3-
[DMBS] with LCST behavior
Number of Hydrogen bonds per O atom
Hydrogen bonds
- Below Tc: 10 oC, 20 oC
- Above Tc: 50 oC, 60 oCRef. critical T = 36 oC at 50 wt.%
MD Running
Timestep : 1.0 fs
Total timesteps : 10 M timesteps = 10 ns for every T cases (after pre-running for equilibration)
Isothermal-Isobaric ensemble (NPT)
• [P4444][DMBS] : 80 pairs of ILs & 1920 water molecules (= 50.8 wt.%)
with LCST behavior
• [P4444][BnzSO3] : 80 pairs of ILs & 1440 water molecules (= 49.6 wt.%)without LCST behavior
Initial placement
Potentials • pair style : lj/cut/tip4p/long, cutoff distance 15 A (LJ),13 A (charge) + pppm algorithm
• bond, angle style : harmonic
• dihedral style : charmm
• special style : amber[G. Zhou et. al., J Phys Chem B, 2007]
[X. He et. al., J Phys Chem B, 2010]
Parameters from
Ideal draw agents should possess
• high osmotic pressure
• being easily regenerated with only low grade heat
• low reverse diffusion, viscosity
• good chemical and thermal stability
• low toxicity
[DMBS]-
[P4444]+
P+
S
[P4444][DMBS] with LCST behavior50 wt.%
[P4444][BnzSO3] without LCST behavior50 wt.%
[BnzSO3]-
[P4444]+
P+
S
0 5 10 150
1
2
3
4
5
cation-anion
g(r)
r (A)o
0 5 10 150
0.5
1
1.5
2
g(r)
r (A)o
0 5 10 150
1
2
3
g(r)
r (A)o
cation-cation
anion-anion
0 5 10 150
0.20.40.60.81
1.2
water-cationg(
r)
2 4 6 80
2
4
6
water-water
g(r)
r (A)o
2 4 6 80
0.5
1
1.5
2
2.5
water-anion
g(r)
r (A)o
r (A)o
a)
b)
c)
d)
e)
f)
T = 10 Co
20 Co
60 Co50 Co
O
HO
H
email: [email protected] (H.Kang) [email protected] (J.J.Urban)
Published as [H. Kang et. al., Comms Chem, 2 (51) 2019]