44th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit AIAA 2008-4533

21 - 23 July 2008, Hartford, CT

Computational Investigation of Mole ular Ion

Evaporation in Ele trospray Thrusters
 y
Nanako Takahashi and Paulo C. Lozano

Massa husetts Institute of Te hnology, Cambridge, 02139, U.S.A.

We present a preminary study on the evaporation of solvated and non-solvated ions

of an imidazolium salt, 1-ethyl-3-methylimidazolium tetra uoroborate (EMI-BF4 ), under
high ele tri elds. Understanding the ion emission me hanism is important in larifying
the performan e of ele trospray thrusters working in the purely ioni regime. Classi al
mole ular dynami s simulations are arried out with the AMBER for e eld in a anoni al
(NVT) ensemble. The diameter of EMI-BF4 droplets is approximately 3 nm, whi h in lude
64 EMI-BF4 mole ules. Solvated ions (EMI-BF4 )n EMI+ and (EMI-BF4 )n BF4 are observed
at elds from 1.0 V/nm through 2.5 V/nm whi h orrespond to experimental data.

Nomen lature

E Potential energy
K For e onstant
r Bond length, A
 Angle, degree
n Multipli ity of fun tion
 Dihedral angle
Phase shift
N Total number of atoms
A Lenard-Jones Parameter
B Lenard-Jones Parameter
R Distan e between two atoms
q Ion harge
 Well-depth
 Size parameter
Subs ript
i Atom i
j Atom j
n Degree of solvation
r Bonds
 Angles
eq Equilibrium state

I. Introdu tion

n re ent years interest in mi rothrusters has been in reasing rapidly due to their potential appli ation for
Ismall-to- medium sized spa e raft. Spe i ally, ele trospray thrusters working in the purely ioni regime are
promising propulsion systems with their pre ise and exible thrust ongurations and performan e in terms
of their high eÆ ien y and multi-modal spe i impulse. One of the hallenges presented in ele trospray
 Graduate Student, Department of Aeronauti s and Astronauti s, 77 Mass Ave 37-362, nanakotmit.edu, AIAA Member.
y Assistant Professor, Department of Aeronauti s and Astronauti s, 77 Mass Ave 37-371, plozanomit.edu, AIAA Member.

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Copyright © 2008 by the American Institute of Aeronautics and Institute
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propulsion is to understand the ee ts of ion evaporation and possible fragmentation in the presen e of
strong ele tri elds. The ion degree of solvation n, the number of neutral ion pairs atta hed to every
positive and negative ion, has an ee t on emitted beam omposition whi h determines the eÆ ien y. Pure
ioni liquids are omposed of just one kind of positive and negative ions that provide a simple onguration
for ion evaporation. The emission hara teristi s from a variety of ioni liquid ion sour es (ILIS) have been
investigated in several experimental studies.1 However, a detailed des ription of the me hanisms driving
ion evaporation in ILIS an not be inferred just from experimental results. Sin e it is ne essary to onsider
intermole ular for es to reveal the behavior of these omplex ions, numeri al simulation by means of mole ular
dynami s (MD) has the potential to larify the pro esses. Landman et al.2 presented unique large-s ale
atomisti simulations ombining ele trohydrodynami s with MD simulation of partial and ioni harges. The
liquid va uum interfa e of formamide salt solutions subje ted to high ele tri elds was investigated. In this
paper, we report the simulation of ion emission from an EMI-BF4 nano-droplet under high ele tri elds.
We fo us on the statisti s of solvated ions using the MD approa h.
II. Simulation Methodology and Model

II.A. For e Field Parameters

The denition of the atomi intera tions or for e elds is one of the most important parts of MD methods
be ause it establishes the behavior of parti les in a lassi al system. We use the for e eld AMBER3 whi h is
widely used in the ioni liquid ommunity. The for e eld parameters whi h are applied to our investigation
for EMI-BF4 mole ules are those suggested by de Andrade et al.4 in whi h a omplete for e eld for liquid-
state simulations of the ioni liquid EMI-BF4 is presented. Potential parameters whi h we take into a ount
for the MD simulations are bond stret hing, bond angle, dihedral torsion, in luding proper and improper
torsions, and nonbonded Van Der Waals potentials. Figure 1 shows the hemi al stru tural formulae whi h
indi ate atom types and partial harges of EMI-BF4, as referred from the results of de Andrade et al.

(a) EMI+ (b) BF4

Figure 1. (a),(b) Chemi al stru tural formulae with atom types and partial harges of EMI+ anion and BF4 ation.

II.B. Computational model

The omputational model is a three-dimensional (3D) system developed with the aim of investigating the
detailed behavior of solvated and non-solvated EMI-BF4 mole ules under ele tri elds. Sin e EMI-BF4 is
a highly unsymmetri mole ule, it is not proper to assume a spheri al for e eld to keep the me hani al
integrity of the mole ule.
The atom oordinates for a single EMI-BF4 mole ule were obtained by the semiempiri al orbital program
MOPAC65 whi h enabled us to obtain the fully optimized Cartesian set of oordinates for all atoms within
the mole ule (See gure 2 on the following page). We verify that this orresponds to the stru ture indi ated
by Katsyuba et al.6 As prepro essing of the simulation, 64 EMI-BF4 mole ules are pla ed arbitrary in a
ubi onguration with the potential parameters des ribed in the previous se tion. The initial oordinates
for the simulations with high ele tri elds are obtained from the equilibrium state at room temperature
T = 300 K. We use the Visual Mole ular Dynami s (VMD) software for visualization and analysis.7 ; 8

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II.C. Mole ular Dynami s Simulation

Classi al Mole ular Dynami s Simulations were performed using the mas-
sively parallelized modeling ode LAMMPS,9 whi h enables us to run on
large omputing lusters. The simulation pro edure in ludes 2 y les for
the optimization of stru tures with ensembles with onstant number of
moles, volume, and energy (NVE) and onstant number of moles, vol-
ume, and temperature (NVT). The simulation in ludes a uniform and
steady high ele tri eld and temperature entral. The NVE simulation
was started from T = 10 K to release ex ess energy stored in the initial
ubi oordinate distribution des ribed in the previous se tion, following Figure 2. Three dimensional stru -
the potential energy of the system (See equation (1)). tural model of the ioni liquid EMI-
BF4
" #
X X X Vn X Aij Bij qi qj
Etotal = Kr (r req )2 + K ( eq )2 + [1+ os(n )℄+ + (1)
dihedrals 2
12
Rij 6
Rij Rij
bonds angles i<j

where
Aij = 4ij ij12
Bij = 4ij ij
6
In this expression, the terms on the right hand side represent, respe tively, the potential energy between
ovalently bonded atoms, the energy due to the angular geometry of ovalent bonding, the energy for
twisting a bond due to bond order, and the non-bonded energy between all atom pairs whi h in lude van der
Walls (Lennard-Jones) and ele trostati potentials, respe tively. The NVE simulation was repeated until
the temperature onverges near room temperature, T = 300 K, from whi h the NVT simulation starts.
The Nose-Hoover thermostat10 is used in NVT simulations with a temperature damping of 100 K. The last
traje tory in the NVE simulation is used for the initial oordinate and velo ity for the NVT simulation.
The whole study is arried out with a uto distan e 200 nm for both the Lennard-Jones and Coulombi
potentials whi h overs all mole ules when those have a droplet onguration. The diameter of the droplet
in its equilibrium state is approximately 3 nm. After equilibrium is rea hed with the NVT simulation, the
nal traje tory is used as the initial ondition for the al ulation with the ele tri eld applied in the x
dire tion. We investigate an EMI-BF4 droplet under high ele tri elds from 1 V/nm through 10 V/nm.
This simulation is arried out with the NVE ensemble. On the other hand, the study for vaporization uses
the NVT ensemble with Nose-Hoover thermostat and a temperature damping rate of T =100 K from room
temperature T = 300 through T = 1200 K. All simulations are performed in a parallelized ode using the
Open MPI library11 ompiled by a GNU C++ ompiler on RedHat LINUX Enterprise 5 under a gigabit and
inniband network with a maximum of 18 nodes in a 76- ore (Dual-Core AMD Opteron Pro essor 2216)
omputer luster. The ion emission al ulation is arried out with a time step 0.1 fs, with non-periodi
boundary onditions and a shrink-wrapping algorithm with a minimum value of 5  106 iterations.
III. Results and Dis ussion

III.A. Ion Emission under High Ele tri Fields

We investigated the emission of ions from isolated nanodroplets under uniform and homogeneous ele tri
elds from 1 V/nm through 10 V/nm. Ion emission is not observed at elds smaller than 1.0 V/nm, although
the droplet elongates its shape in the dire tion of the eld. In terms of solvated ions, those are not observed
at elds higher than 2.5 V/nm.
We fo us on observing the emission out ome with ele tri elds between 1.0 V/nm and 2 V/nm and
gather the statisti s of non-solvated and solvated ions.
Figure 3 on the next page shows snapshots in hronologi al order of the extra tion pro ess of non-solvated
and solvated ions, (EMI-BF4)nEMI+ and (EMI-BF4)nBF4 in whi h n indi ates the degree of solvation, from
a neutral EMI-BF4 droplet under an ele tri eld of 1.5 V/nm. Ions with the highest degrees of solvation are
shown in Figure +4 on the following page. In these ases, we observed both non-solvated and solvated ions,
(EMI-BF4)nEMI (n = 0, 1, 3) and (EMI-BF4)n BF4 (n = 0, 1, 3).

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 (a) 0 ps. (b) 22.7 ps. ( ) 29.5 ps.

(d) 41.8 ps. (e) 106.4 ps. (f) 114.8 ps.

Figure 3. Ion emission from EMI-BF4 droplet at 1.5 V/nm. (a) Initial state. (b)Neutral state before ion emission.
( ) Emission of EMI+ . (d) Emission of BF4 . (e) Emission of (EMI-BF4 )1 BF4 solvated ion. (f) Emission of (EMI-
BF4 )1 EMI+ solvated ion.

Some solvated ions are emitted as doubly

harged ions, (EMI-BF4)n (BF4)22 , and break up
approximately 3-4 nm upon emission as shown in
Fig. 4 (a) and (b).
At ele tri eld ases of 1.25 V/nm and higher,
solvated ions start to appear after an alternate emis-
sion of at least 3 pure single EMI+ and BF4 ion
emissions. On the other hand, at 1.2 V/nm, the
rst emission is that of a solvated ion. First emis-
sion o urs at about 10 ps with ele tri eld higher (a) 69.7 ps. (b) 83.5 ps.
than 1.2 V/nm, however this in reases to about 100 Figure 4. Ion emission from EMI-BF4 droplet at 1.7 V/nm.
ps at ele tri elds smaller than 1.2 V/nm, whi h (a) Emission of (EMI-BF4 )3 EMI+ . (b) Emission of (EMI-
means it takes 10 times as mu h time as other ases. BF4 )3 BF4 .
The droplet gradually elongates from its initial on-
dition, then ions are emitted from the edge along 


the x dire tion. ! 

Figure 5 shows the average net urrent through 
 "!# # 

ea h ele tri eld simulation whi h indi ates how

many harged ions are emitted per unit of time. The
urrent is obtained using 5 ions and the time
t 


at whi h 5 ions leave from droplet. Also, statisti s 

µ

of non-solvated and solvated ions for both negative 

 


BF4 and positive EMI+ ions are shown in Figure 6 

(a) and (b). Spe i ally, stable and long lasting


 


emission is observed at 1.3 V/nm. At this ele tri
eld, the droplet remains without separation into
small neutral parts. 


The droplet breakup o urs at 136.6 ps at 1.5

V/nm, and 27 ps at 2 V/nm, but it is 460 ps at 




 
1.3/nm. Ele tri elds higher than 1.7 V/nm pro-
    
 
vide more urrent, but it does not last long as the
Figure 5. Average urrent by ion emission

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droplet break-up produ ing neutral mole ules.
We observe ions with degrees of solvation n = 0, 1, 2, 3, 4 for negative BF4 and positive EMI+ and the
total number of ions of ea h type is about the same for all ele tri elds.
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(a) (EMI-BF4 )n EMI+ ion. (b) (EMI-BF4 )n BF4 ion.

Figure 6. Statisti s for Solvated and non-solvated ions (n: Degree of solvation).

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Figure 7. Ele tri eld vs. Distan e from enter of droplet Figure 8. Temperature transition of de omposition simula-
in Sphere-on- one model tion

Emission of neutral mole ules o ur upon frag-

mentation of solvated ion just after emission from
the droplet and also when it breaks into many par-
ti les. However, ele tri elds drop inversely pro-
portional to a distan e from enter of a droplet in
real ones (See gure 7). We use sphere-on- one
model to avoid ounting neutral ions whi h suppose
to be solvated ions under smaller ele tri eld. We
he ked the fragmentation using traje troies and o-
ordinates of a single solvated ions referring ele tri
elds from distan e from gure 7.
Some ions are not emitted along the x dire tion, (a) (b)
but in a radial pattern with an angle of approxi-
mately 10 degrees. The CPU times for ea h sim- Figure 9. De omposition of an EMI-BF4 droplet. (a) Neu-
tral state droplet at approximately T = 690 K. (b) Neutral
ulation depend on how many ions remain within mole ule de omposition at approximately T = 1100 K.
the uto distan e. The fastest CPU time is 738
minutes, with an ele tri eld of 2.0 V/nm using 4
nodes, while the slowest takes more than 168 hours
with an ele tri eld smaller than 1.2 V/nm.
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III.B. De omposition Temperature

The EMI-BF4 droplet used in the ion emission experiment was also used to gure out the de omposition
temperature in the ondition outlined in se tion II.C. Figure 8 on the pre eding page shows the temperature
prole applied to the droplet. Snapshots in the pro ess of de omposition are shown as verti al lines. These
orrespond to the simulation results shown in Figure 9 on the previous page. The de omposition o urs at
T =1098.4 K at whi h a neutral mole ule disso iates from the droplet. The rst ions were emitted approxi-
mately at 310 K under an ele tri eld, whi h means that the ion emission is not ae ted by temperature at
that point. However, on e it rea hes the de omposition temperature, there is a higher possibility to separate
into smaller neutral droplets whi h do not ontribute to ion emission.
IV. Con lusion and Future Work

Mole ular dynami s simulations are arried out to investigate the detailed behavior and statisti s of 3
nm ioni liquid EMI-BF4 droplets. Solvated ions are observed under ele tri elds between 1.0 V/nm and
2.5 V/nm. The largest number of emitted ions were observed at 1.3 V/nm. Non-solvated ions emitted the
most under all ele tri elds, and is observed in all ases. The highest degree of solvation is n = 4 whi h is
shown in both BF4 and EMI+ solvated ions. Future work will in lude investigation over a more extensive
ele tri eld range. It is also ne essary to perform the simulation with larger droplets by in luding more
mole ules and avoid qui k depletion. We also require a more a urate ele tri eld model to simulate more
pre isely what happens in real ones where the eld in a droplet falls as 1=r2 and in a Taylor one, whi h
falls as r1=2 .
V. A knowledgement

We a knowledge kindful and helpful for e eld dis ussions with Professor Stassen. We further a knowl-
edge simulating dis ussions with Professor Buehler and R. Shahsavari.
Referen es

1 Lozano, P., Martinez-San hez, M., \EÆ ien y Estimation of EMI-BF4 Ioni Liquid Ele trospray Thrusters", 41st
AIAA/ASME/SAE/ASEE Joint Propulsion Conferen e & Exhibit, AIAA paper 2005-4388, Tu son, Arizona, July 10-13, 2005
2 Landman, U., Oral presentation, MIT 3rd Ele trospray Workshop, Department of Aeronauti s and Astronauti s, MIT,
Cambridge, Massa husetts, 2005
3 Cornell, W.D., Cieplak, P., Bayly, C. I., Gould, I.R., Merz, K. M., Jr., Ferguson, D. M., Spellmeyer, D. C., Fox, T.,
Caldwell, J. W., Kollman, P. A., \A Se ond Generation For e Field for the Simulation of Proteins, Nu lei A ids, and Organi
Mole ules", Journal of Ameri an Chemi al So iety, Vol. 117, 1995, pp. 5179-5197
4 de Andrade, J., Boes, E. S., Stassen, H., \Computational Study of Room Temperature Molten Salts Composed by 1-
Alkyl-3-methylimidazolium Cations { For e-Field Proposal and Validation", Journal of Physi al Chemistry B, Vol. 106, 2002,
pp. 13344-13351
5 Stewart, J. J. P., \MOPAC: A semiempiri al mole ular orbital program", Journal of Computer-Aided Mole ular Design,
Vol. 4, No. 1, 1990, pp. 1-103
6 Katsyuba, S. A, Dyson, P. J., Vandyukova, E. E., Chernova, A. V., Vidis, A., \Mole ular Stru ture, Vibrational Spe tra,
and Hydrogen Bonding of the Ioni Liquid 1-Ethyl-3-methyl-1H-imidazolium Tetra uoroborate", Helveti a Chimi a A ta, Vol.
87, 2004, pp. 2556-2565
7 Stone, J., Gullingsrud, J., Grayson, P., S hulten, P., \A system for intera tive mole ular dynami s simulation", 2001
ACM symposium on Intera tive 3D Graphi s, edited by J.F. Hughes and C.H. Sequin, ACM Press, New York, 2001, pp. 191-104
8 Humphrey, W., Dalke, A., Shulten, K., \VMD: Visual mole ular dynami s", Journal of Mole ular Graphi s, Vol. 14, No.
33, 1996
9 Plimpton S., \Fast Parallel Algorithms for Short-Range Mole ular Dynami s", Journal of Computational Physi s, Vol.
117, 1995, pp. 1-19
10 Martyna, G. J., Tu kerman, M. E., Tobias, D. J., Klein, M. L., \Expli it reversible integrators for extended systems
dynami s", Mole ular Physi s, Vol. 87, No. 5, 1996, pp. 1117-1157
11 Graham, R. L., Shipman, G. M., Barrett, B. W., Castain, R. H., Bosil a, G., Lumsdaine, A., \Open MPI: A high-
performan e, heterogeneous MPI", Pro eedings, Fifth International Workshop on Algorithm, Models and Tools for Parallel
Computing on Heterogeneous Networks, Bar elona, Spain, September, 2006

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