Article

pubs.acs.org/JPCC

Structure of Quaternary Ammonium Ionic Liquids at Interfaces:

Effects of Cation Tail Modification with Isoelectronic Groups
Shobha Sharma and Hemant K. Kashyap*
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
*
S Supporting Information

ABSTRACT: Herein we use molecular dynamics simulations to

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investigate the effects of cation tail modification with isoelectronic

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groups on interfacial structure of room-temperature ionic liquids

(RTILs) when confined between two oppositely charged or two
neutral graphene sheets. The RTILs chosen in this regard are
triethyloctylammonium bis(trifluoromethylsulfonyl)imide (N2228+/
NTf 2 − ) and (2-ethoxyethoxy)ethyltriethylammonium bis-
(trifluoromethylsulfonyl)imide (N222(2O2O2)+/NTf2−). For all the
systems studied, we determined number density, free energy, electric
field and electrostatic potential profiles along the axis normal to
graphene sheet plane. Our results predict that in both the systems,
the positively charged graphene sheets are screened predominantly
by anionic atoms and cationic tail groups that are embedded in the
cavities formed by the anions in the interfacial region, and the extent of screening for the RTIL containing alkyl-substituted
cations is slightly higher than that in the diether-substituted analog. Near the negatively charged sheet, while the probability of
finding cation tails is relatively enhanced in the diether system, increased density augmentation of cation head groups in the
N2228+ system is observed in comparison with that in the N222(2O2O2)+ system. We observe both perpendicular and parallel
orientations of cation tail near the negatively charged wall, but it appears that the probability of parallel orientation for
N222(2O2O2)+ is higher than that for N2228+. In the case of neutral sheets, the anionic distribution at the interface is similar in both
the cases and cation tail enrichment in the first layer close to the neutral wall is increased in the system with a non-polar tail. The
probability of finding cation head groups in the vicinity of neutral wall is slightly larger in the case of diether system. The
simulated zone-resolved tangential radial distribution functions (TRDFs) in planar slabs parallel to the sheets show that the
cation heads (or anions) in the interfacial region closest to the negatively (or positively) charged sheet are ordered more than
that in the corresponding bulk liquid. For both the isoelectronic analogs, the overall charge density fluctuations and electric field
oscillations near the positively charged walls are larger than that near the negatively charged walls.

1. INTRODUCTION can be found on RTILs with cation consisting of polar

Room-temperature ionic liquids (RTILs) have recently
revolutionized a broad area of scientific research and industrial
applications. Ionic liquid (IL) that is composed only of ions and
is liquid below 100 °C is now widely accepted as room-
temperature ionic liquid. RTILs are equipped with several
exquisite properties, such as high thermal stability, low
volatility, substantial ionicity, wide electrochemical window,
tunable hydrophobicity and hydrophilicity, tunable Lewis
acidity and non-flammability.1,2 In past few years, RTILs have
also been thought of as good electrolytes for their uses in
batteries, photo-electrochemical cells, electroplating, and
capacitors.3,4 Properties of RTILs can be changed by modifying
the chemical nature of constituent cation and/or anion. This
makes RTILs stand in the category of promising solvents and
increases the area of their applications. These applications may
also include their uses in biological research, synthesis, catalysis
and heat storage. Until very recently, RTILs composed of
cations with non-polar alkyl tail of different length were most
studied and thoroughly understood.5−7 Only a few endeavors
functional group(s).8−12 RTILs with polar tails appear to be
less viscous and better ionic conductors.13 Experimentally it has
been observed that such modification of cationic tail improves
the kinetic performance of RTILs and thus make these RTILs
to be used as electrolytes in energy efficient devices, like
electrochemical cells, dye sensitized solar cells and super
capacitors.3,4,14−19 However, such potential applications of
these novel category of RTILs warrant a molecular-level
understanding of their structural organization and dynamics
not only in bulk phase but also at RTIL/electrode
interfaces.20,21 In this work, we are aiming to characterize the
interfacial properties of ammonium-based RTILs with a polar
and a non-polar cationic tail. The attention is on understanding
the effects of cation tail mutation with isoelectronic groups on
the structural patterning of RTILs in the interfacial region close
Received: July 6, 2015
Revised: September 24, 2015
Published: September 28, 2015

© 2015 American Chemical Society 23955 DOI: 10.1021/acs.jpcc.5b06460

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to the charged and neutral walls. This work will also provide a
clear description of the charge alternation as well as the polar−
nonpolar alternation at RTIL/electrode interfacial region.
Theory of structural patterning to describe the electrostatic
properties of diluted electrolyte solution at electrified interfaces
starts with those of Gouy, Chapman, and Stern.22 It is now
known that this classic theory works well for dilute electrolyte
solutions, but in the cases where molecular length scales and
shape are important factors, such primitive model based
theories are not adequate, and concept of electrical double-
layer is also not applicable. 20,23−31 Recently, neutron
reflectometry, cyclic voltammetry, and differential capacitance
measurements25 have revealed that the interface between ionic
liquid and positively charged gold surface was cation rich. This
observation, that contradicts the classical double layer theory,
indicates a non-electrostatic adsorption of cations onto gold
electrode.25 Therefore, a comprehensive molecular level
understanding of such interfaces is crucially important for the
optimal utilization of the novel features related to such
interfaces for their desired properties in interface-based
applications.20,23,24,32−35 For example, the efficiency of electron
transfer or redox reactions that occur in electrochemical devices
is governed by the interfacial region near the electrode.36−38
In this context, molecular dynamics (MD) simulation studies
done by Lynden-Bell and co-workers on representative
imidazolium ionic liquids confined within charged and neutral
graphene sheets were focused on elucidation of structural
arrangement of ionic species near such walls.39,40 According to
Wang et al., the arrangement of ionic species near interfacial
region depends on the charge of ionic species, charge on wall
and chemical structure of the ionic species.41 As described by
Martin et al., the layered structure of the constituent ions of
RTILs near charged walls could also be due to overscreening or
crowding, depending upon the voltage applied. At lower
voltage, overscreening is prominent, and if we keep on
increasing the voltage, overscreening may turn into crowding.
In the systems studied here, no sign of crowding of the counter-
ions near the charged wall−ionic liquid interface is observed,
but screening of the charged sheets can be noticed.42,43 This
observation is not surprising as the charge density on graphene
sheet used in this study (±1 e nm−2) is of medium strength.
In pursuit of developing a concrete understanding of RTIL/
electrode interfacial structure, an extensive amount of other
MD simulation studies have been done in the recent
past26,44−52 and almost all of them were focused on
imidazolium based RTILs. Compared to well-known imidazo-
lium ionic liquids, quaternary ammonium ionic liquids are
electrochemically more stable toward oxidation and reduction,1
and therefore can be considered as good electrolyte for high
energy storage devices. Recently, Shirota et al.13 synthesized
quaternary ammonium/phosphonium based RTILs along with
their isoelectronic diether analogs and observed that the diether
substituted RTILs possess lower viscosity.13 RTILs with lower
viscosity and improved conductivity are crucially important for
their uses in energy-application devices.13,18,53,54 Recently, the
microscopic structure and dynamics of these RTILs were
studied by using X-ray scattering,12 NMR,55 dielectric spec-
troscopy and quasi-elastic light scattering spectroscopy56 along
with MD simulations.12,13 On the basis of these studies, it is
now established that RTILs containing diether-substituted
cations do not show intermediate range ordering and thus do
not possess polar-nonpolar alternating domains that are often
present in RTILs with moderately long alkyl-substituted cation
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tails.11,12,57−62 In this work, we have performed molecular
dynamics simulations of N2228+/NTf2− and N222(2O2O2)+/NTf2−
RTILs (see Figure 1) confined between two oppositely charged
Figure 1. Chemical structure of (a) triethyloctylammonium (N2228+)
(b) (2-ethoxyethoxy)ethyltriethylammonium (N222(2O2O2)+), and (c)
bis(trifluoromethylsulfonyl)imide (NTf2−) ions. The positive charge
distribution on the N2228+ cation is localized near head groups and the
cation longest tail is overall electrically neutral.12 However, this is not
the case for N222(2O2O2)+; the positive charge is well spread over the
cation head and tail groups.12
or two neutral graphene sheets to appreciate how these RTILs
respond to confinement and external stimulus such as electric
field. The charge density for the charged graphene sheets were
taken as ±1 e nm−2 and neutral walls possessed zero charges on
the carbon atoms of the graphene sheets.
2. SIMULATION DETAILS
Molecular dynamics simulations for N2228+/NTf2 − and
N222(2O2O2)+/NTf2− RTILs confined between either two
oppositely charged or two neutral monolayered graphene
walls were performed in the canonical (NVT) ensemble by
using GROMACS 4.6.5 package.63,64 The chemical structures
of N2228+ and N222(2O2O2)+ cations are shown in Figure 1a,b,
respectively. The anion (NTf2−) is depicted in Figure 1c. The
temperature of all the systems was set to 292 K using a velocity-
rescale65 thermostat. For all the systems studied, a previously
equilibrated12 box of RTIL with 1000 ionic-couples was
carefully replicated along the z-axis, leading to a rectangular
parallelepiped box with 2000 ionic-couples. The dimensions of
the graphene sheets, constructed by using Visual Molecular
Dynamics (VMD) package,66 were chosen according to the
side-lengths of RTIL boxes along x and y directions. In case of
N2228+/NTf2− system, the graphene walls were placed at z = 0
and z = 18.24 nm (see Figure 2a,b). For N222(2O2O2)+/NTf2−
system, the two walls were placed at z = 0 and z = 17.674 nm
(see Figure 2c,d). In case of charged walls, the wall at z = 0 was
positively charged with +1 e nm−2 charge density and the other
wall was negatively charged with −1 e nm−2 charge density. For
neutral walls, both the walls were kept at zero charges. A
vacuum of half of the box-length in the z-direction was used to
avoid interaction between the negative wall of one image to the
positive wall of another image (Figure 2). Please see the
Supporting Information for the whole set of box dimensions
used in the simulations. The Lennard-Jones (LJ) and bonded
parameters for the graphene sheet atoms were adapted from
those given by Trinidad et al.;39 ϵ = 0.29288 kJ mol−1,σ = 0.355
nm, r0 = 0.142 nm. Parameters for bis(trifluoromethylsulfonyl)
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Figure 2. Equilibrium snapshot for (a) N2228+/NTf2− ionic liquid confined within charged graphene walls (blue = positively charged and red =
negatively charged) (b) N2228+/NTf2− ionic liquid confined within neutral graphene walls (cyan = neutral) (c) N222(2O2O2) +/NTf2− ionic liquid
confined within charged graphene walls (d) N222(2O2O2) +/NTf2− ionic liquid confined within neutral graphene walls. Here the oxygen atoms of
N222(2O2O2)+ cation are depicted in red. The cations and anions are shown in lime and orange colors, respectively. The dimensions of the boxes
provided in the figures are in units on nanometers.

Figure 3. Number density (relative to bulk number density), as a function of distance z from the positively charged graphene wall for (a) N2228+/
NTf2− and (b) N222(2O2O2)+/NTf2− RTILs. We have used about 5000 slices to define the bin-width in the above graphs.

imide NTf2− anion, triethyloctylammonium N2228+ and (2-
ethoxyethoxy)ethyltriethylammonium N222(2O2O2)+ cations were
used from Lopes and Pádua67,68 (CLaP) and all-atom
optimized potential for liquid simulations (OPLS-AA) force-
fields.69−72The full set of parameters for these RTILs can be
found in the Supporting Information of ref 12 along with the
Supporting Information of the present article. Keeping the
spirit of OPLS-AA type combination rules, all the cross terms
for LJ interactions were approximated as ϵij = (ϵiϵj)1/2 and σij =
(σiσj)1/2. Proper periodic boundary conditions and minimum
image convention were applied. Electrostatic interactions were
computed by using particle-mesh Ewald (PME) summation73
technique together with Yeh-Berkowitz correction for the slab
geometry.74 The velocity-verlet integration algorithm with a
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time-step of 1 fs was used for integrating equations of motion
of RTIL atoms. Atoms of graphene sheets were frozen to their
equilibrium bond distance during the simulations. The cutoff
radius for the short-range interaction and the real-space part of
electrostatic interaction was set to 12 Å. For PME summation
interpolation order of 6 and Fourier grid spacing of 0.8 Å was
employed. The equilibration run for N2228+/NTf2− and
N222(2O2O2)+/NTf2− systems were of 25 and 35 ns, respectively.
Atomic velocities were randomly generated at 292 K from a
Gaussian distribution at the very first step of the equilibration
run. Finally production run of another 10 ns was carried out
and the trajectories were saved at every 100 fs for computing
the density profiles, radial distribution functions and other
properties.
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Figure 4. Number density (relative to bulk number density) as a function of distance z from the negatively charged graphene wall for (a) N2228+/
NTf2− and (b) N222(2O2O2)+/NTf2− RTILs. We have used about 5000 slices to define the bin-width in the above graphs.

Figure 5. Number density (relative to bulk number density) as a function of distance z from the neutral graphene wall for (a) N2228+/NTf2− and (b)
N222(2O2O2)+/NTf2− RTILs. Also, see Figure S2 for more details. We have used about 5000 slices to define the bin-width in the above graphs.

3. RESULTS AND DISCUSSION
3.1. Number Density Profiles. In order to analyze the
ionic distribution or structural patterning at the interface
between RTIL and graphene wall, in Figures 3−5 we have
depicted the number density profiles, ρn(z), for cation head,
cation tail and anion atoms as a function of distance (z) from
the wall. The density profiles for cation head and tail were
computed by using center-of-mass coordinates of the cation
head and cation longest tail groups (see Figure 1 for the exact
definition of cation head and tail groups) . The first feature to
be observed from these figures is that for the charged systems,
all the profiles show pronounced oscillations, the so-called
layering, that last up to ∼1.5 nm distance from the graphene
sheets. However, near neutral graphene walls these density
oscillations are apparent only up to ∼1.2 nm.
Parts a and b of Figure 3 show that number density
augmentation for anion oxygen is maximum and is nearest to
the positively charged sheet in both the systems. The first peak
position for the anion oxygen atom is at around 0.3 nm from
the wall. At around same distance the probability of finding
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fluorine atoms of anion is also more than its bulk value. Beyond
these peaks the triplet peaks in the range of 0.3−0.5 nm for
anion nitrogen atoms can also be observed. This tells us that
the first layer of the RTILs near the positively charged wall
predominantly consists of anion atoms for both the systems. A
careful investigation of the interaction terms for the cation and
anion atoms reveals that the strong affinity of oxygen atoms
toward the wall is due to both nonpolar (LJ) and electrostatic
interactions. Although anion distribution near the positively
charged wall looks similar in the density profiles for both the
RTILs, there are differences in the cation head and tail
distributions in the alkyl and diether substituted systems. It is
clear that the most prominent peak for cation tail appears at
∼0.4 nm, before any peak that belongs to cation head for both
the RTILs. This infers that on average there is dominance of
cationic tail groups that are oriented toward the positively
charged walls in both the systems. From these figures, Figure 3,
parts a and b, it is clear that overall orientation of the charged
species in both the systems near the positively charged wall
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Figure 6. Potential of mean force, A(z), as a function of distance z from the neutral graphene wall for (a) N2228+/NTf2− and (b) N222(2O2O2)+/NTf2−
RTILs.
follows the order: anion oxygen ∼ anion fluorine > anion
nitrogen > cation tail > cation head.
Density profiles near the negatively charged walls depicted in
Figure 4, parts a and b, clearly have two dominant peaks nearest
to the wall, at ∼0.4 nm and ∼0.45 nm. The closest peak
belongs to cation tail (red) and the peak to it corresponds to
cation head (black). As will be more clear later on, the closest
peak belongs to cation tails that are parallel to the wall. The
cation head peak has head facing toward the wall and the tails
associated with these heads are oriented both parallel and
perpendicular to the wall. One can also observe another cation
tail peak at ∼0.5 nm for the diether system. A closer look of the
simulation snapshots confirmed that this peak belongs to tails
that are slightly tilted outward from the wall. Hence, for both
the systems the first interfacial layer near the negatively charged
graphene predominantly consist of cations. The subsequent
layer in the alkyl-substituted system is broader and composed
of cation tails and anions with no preferential orientation. But,
in the case of diether system the second layer is comprised of
cation head, cation tail as well as anions. The probability of
finding the cation tails near negatively charged graphene sheet
in the diether system is more than that in its alkyl-substituted
analog. The ordering of the groups for both the systems near
the negatively charged wall follows as cation tail > cation head
> anion oxygen > anion fluorine > anion nitrogen. To
investigate further details, number density profiles for nitrogen
atom of cation head and three terminal carbon atoms of three
ethyl tails were also calculated (see Figure S1). It was found
that these ionic subunits are arranged near the negatively
charged wall in the following order: cation head terminal
carbons > cation tail > cation nitrogen > anion oxygen > anion
fluorine > anion nitrogen. This implies that the approach of
nitrogen atom, which is equivalent to cation head center-of-
mass, of cation head toward negatively charged wall is hindered
by three ethyl tails of the cation. The appearance of cation tail
peak before cation head peak in the number density profiles is,
therefore, due to steric shielding effects.
For the systems confined between neutral walls (Figure 5a,b)
one can observe that even in absence of external electric field,
neutral graphene surfaces lead to certain structural patterning of
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the confined RTIL, indicating significance of nonpolar (LJ)
interactions between the wall and constituent species of the
RTIL. At least three layers of ionic species are apparent up to
1.2 nm and beyond that corresponding bulk densities are
recovered. The interfacial layer in this case consists of both
cations and anions. The order of closest approach to the neutral
walls for both system is anion fluorine > anion oxygen > anion
nitrogen > cation tail > cation head. Since LJ parameters are
closely related to atomic polarizabilities and atomic charge
densities, we can explain this ordering on the basis of σ, the
distance of closest approach, and ϵ values of the constituent
atoms. As we can see from Table S2 in the Supporting
Information, the position of the first peak in the number
density profiles for the RTIL atoms corresponds to their
respective σ values and the peak height and area under the peak
are governed by both σ and ϵ values as well as electrostatic
interaction between constituent ionic species. We also notice
that cationic tail modification with isoelectronic group does not
render any significant effect on structural ordering of the RTILs
near the neutral walls, except that the probability of cation head
being near to the wall is slightly higher in the diether-
substituted system. To summarize, when we compare charged
and neutral systems, there are differences in the peak positions
and peak heights because the charges on the graphene walls
lead to molecular recognition. In charged systems, negative
species are closer to the positively charged wall; positive species
are closer to negatively charged wall, for screening of charges
on the walls. Near the negative/positive wall, the surplus of
cationic/anionic species that counterbalances the charge on the
respective electrode attracts oppositely charged ions that in
turn propagate the formation of the second layer of lower peak
height. This process of formation of layered structure continues
almost up to 1.5 nm, after which bulk density is achieved. These
observations corroborate well with other studies.26,39,40,44−51
3.2. Potential of Mean Force. The amount of energy
required to bring a given group or atom of RTIL from bulk to
close vicinity of wall as a function of distance can be computed
using potential of mean force (PMF), A(z), as
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Figure 7. Potential of mean force, A(z), as a function of distance z from the positively graphene wall for (a) N2228+/NTf2− and (b) N222(2O2O2)+/
NTf2− RTILs.
Figure 8. Potential of mean force, A(z), as a function of distance z from the negatively charged graphene wall for (a) N2228+/NTf2− and (b)
N222(2O2O2)+/NTf2− RTILs.
ρn (z)
A(z) = −kBT ln
ρnBulk (1)
Here ρn(z) is number density of the given species as a function
of distance from the graphene sheet and ρBulk is its bulk density.
n
It is easy to conceive from Figures 6−8 that for all the systems
studied, the PMFs show oscillatory behavior in close vicinity of
the walls. The cation head PMFs also show tremendously large
(divergent) barriers near 0.5−0.8 nm while approaching toward
the positive wall (Figure 7) and at almost the same range the
anion nitrogen PMFs show similar behavior while approaching
to negative wall (Figure 8).
For neutral walls, parts a and b of Figure 6 show that cation
head and cation tail PMF profiles show deep minima near the
interfacial region in both the systems, this is not the case for the
anion atoms in the region (Figure S3). This observation
indicates that the cationic groups are more preferred near the
neutral walls and nonpolar interactions dominate in the
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interfacial region of neutral walls. Also, the distance of closest
approach for cation heads or cation tails are same in both the
analogs. That is the distance of closest approach to the wall is
not influenced by the tail modification. But the strength of
attraction and repulsion for cation head as well as cation tail are
different in both systems as they approach the neutral walls.
Remarkable oscillations in the PMFs of anion atoms near
positive wall can be seen in parts a and b of Figure 7. Anion
atoms have higher preference toward the positive wall (Figures
7a,b) in both systems and are located at approximately equal
distance from the positive wall, indicating the influence of
electrostatic interaction between the wall and anion atoms. The
oxygen atoms of the anion is most likely to be present near the
wall in comparison to other atoms of the anion. Except fluorine,
all atoms of anion encounter very large barrier at around 0.5−1
nm.
From Figure S4 in the Supporting Information when we
compare the results for cation head and tail PMFs near the
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Figure 9. Tangential radial distribution functions (TRDFs) as a function of distance r for (a) cation nitrogen atom in N2228+/NTf2− system in the
first zone near the interfacial region of the negatively charged graphene wall and (b) cation nitrogen in N222(2O2O2)+/NTf2− system in the first zone
near the interfacial region of the negatively charged graphene wall (c) anion nitrogen in N2228+/NTf−2 system in first zone near interfacial region of
the positively charged graphene wall and (d) anion nitrogen in the N222(2O2O2) +/NTf−2 system in first zone near interfacial region of the positively
charged graphene wall. Here, each TRDF is compared with its corresponding RDF obtained in the corresponding bulk RTIL.

positive wall, we find that cation tails in both the system are
preferentially pulled toward the positive wall and cation heads
are pushed away from the wall. This is evident as the separation
between cation tail and cation head first minima of the PMFs is
large near the positively charged wall. Also the potential energy
barriers for the cation tail in the 0.5−0.8 nm range is lower in
the alkyl system than that in the diether RTIL. Near the
negatively charged graphene, we observe that the cationic
groups are more preferred near the wall (8a,b) and the anion
locations under shallow potential are shifted to longer distances
from the wall (Figure S5). Obviously, cationic tails of diether
RTIL are more likely to be present near the negatively charged
sheet in comparison to that of the alky tail RTIL.
3.3. Tangential Radial Distribution Functions. To
elucidate the pair correlations between co- and counterions in
planar slabs parallel to the graphene sheets, we computed zone-
resolved tangential radial distribution function75,76 (TRDF)
using eq 2
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∑i , j δ(r − rij)
gij(r ) = ; zij < Δz
2πρregion dr Δz (2)
where ρregion = Nregion/(ΔzLxLy) is average number density in
each region and rij = xij 2 + yij 2 . The slab width Δz is usually
set to 0.5 nm for proper statistical averages.75,76
Parts a−d of Figure 9 show TRDFs for cation nitrogen and
anion nitrogen atoms in the interfacial slab nearest to the
negatively and positively charged walls, respectively. These
TRDFs are also compared with corresponding radial
distribution functions (RDFs) in the bulk RTIL.12 The slabs
chosen here were centered at the corresponding number
density peak with maximum heights. From Figure 9, it is clear
that for both the RTILs the tangential correlations of cationic
(or anionic) nitrogen atoms in the interfacial region closest to
the negative (or positive) wall are stronger than that in the bulk
region. This means that the interfacial region is more ordered
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Figure 10. Snapshot representing the anions and cations of (a) N2228+/NTf2− and (b) N222(2O2O2)+/NTf2− near the positively charged graphene.
Isosurfaces representing the subvolume occupied by the anionic network in N2228+/NTf2− (c) and N222(2O2O2)+/NTf2− (d) near the positively
charged graphene sheets. Isosurfaces representing the subvolume occupied by the anionic network and cations of N2228+/NTf2− (e) and the same for
N222(2O2O2)+/NTf2− (f) near the positively charged graphene. Here, blue colored wall is positively charged graphene. Alkyl tails of cation are shown in
lime color. In the cation molecules, nitrogen atoms are highlighted as blue spheres and oxygen atoms of diether alkyl tail of N222(2O2O2) + cations are
highlighted as red spheres. In anion molecules, fluorine atoms are shown in pink, nitrogen atom in blue, oxygens in red, sulfur atoms in yellow and
carbon atoms are shown in cyan color. Hydrogen atoms of cations are hidden for clarity. Only a cross-section of the simulation boxes are shown here.

than the bulk for both the RTILs, i.e., the cation head (or
anion) packing in the interfacial region of the negatively (or
positively) charged graphene wall is more than that in the
corresponding bulk liquids.
3.4. Equilibrium Snapshots and Isosurfaces. The
overall structural features obtained in the density profiles and
TRDFs in the previous subsections are supported and can be
appreciated more clearly by looking at the isosurfaces of the
ions (Figures 10 and 11). In these figures we present a pictorial
demonstration of anion and cation atom distribution in the
interfacial region of charged walls by using isosurfaces. As
apparent from Figure 10a,b, the first layer near positively
charged sheet is anion-rich and the major axis of symmetry of
the anions is mostly parallel to the wall, also showing the
dominance of electrostatic interactions between anion oxygen
and graphene sheet. From parts c and d of Figure 10, it is
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evident that the anions in the interfacial layer nearest to the
positively charged sheets are not homogeneously distributed
and instead they form a well connected network, wherein there
are cavities of irregular shapes. Smaller cavities are observed in
the case of N222(2O2O2)+/NTf2− and mostly the cation tails are
embedded in these cavities in both systems (Figure 10e,f).
Clearly, these anionic networks and cavities are absent near the
negatively charged walls (Figure 11a,b). As can be seen in parts
c and d of Figure 11, for the N2228+/NTf2− system near the
negatively charged wall, most of the cation tails are
perpendicular to the graphene sheet, but a non-negligible
parallel orientation of the cation tail can also be seen in the
snapshots. In the N222(2O2O2)+/NTf2− system, due to presence
of oxygen atoms and gauche kinks12,77 in the cation tail, the
tails are not perfectly perpendicular to the wall and in most
cases both the oxygen atoms of the cation tail are oriented
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Figure 11. Isosurfaces representing the subvolume occupied by the anions of N2228+/NTf2− (a) and N222(2O2O2)+/NTf2− (b) near the negatively
charged graphene sheets. Snapshot representing the anions and cations of N2228+/NTf2− (c) and the same for N222(2O2O2)+/NTf2− (d) near the
negatively charged graphene. Here, red colored wall corresponds to negatively charged graphene. The color coding for other atoms shown here is
same as in Figure 10. Only a cross-section of the simulation boxes are shown here.

parallel to the positively charged graphene wall, only a few d2Ψl (z) ρc (z)
cationic tails oriented normal to the graphene sheet can be 2
=−
dz ε0 (3)
observed in the diether system (Figure 10e,f). From Figure 11
it is quite apparent that while N2228+ tails are orientated both one can estimate El(z) and Ψl(z) as
parallel and perpendicular to the graphene sheet, N222(2O2O2)+ z
∫0 ρc (z) dz
tails are mostly aligned with the negatively charged graphene. E l (z ) =
This observation is not surprising because of the fact that the ε0 (4)
diether tail of N222(2O2O2)+ can have several gauche kinks and z z′
1
the carbons atoms directly bonded to the oxygen atoms possess Ψl (z) = −
ε0
∫0 d z′ ∫0 ρc (z″) dz″
positive charges.12 On the other hand, the alkyl tail of N2228+ (5)
mostly renders trans dihedrals.12 We also observe that the Here ε0 is vacuum permittivity, ρc(z) is liquid charge density (in
anion density pattern near the negatively charged graphene e/nm3) as a function of distance, z. El(z) and Ψl(z),
sheet is similar for both the RTILs but cation density pattern is respectively, are the electric field and electrostatic potential
different. due to the charge distribution of the RTILs. The external
3.5. Electrostatic Properties. Profiles for the electrostatic electric field (E0) and electrostatic potential (Ψ0) due to walls
|σ | |σ |
potential, Ψl(z), and electric field, El(z), along the direction of can be estimated via E0(z) = εs and Ψ0(z) = − εs z = −E0z ,
applied field can be computed from the liquid charge density
0 0
respectively. Here, σs is the surface charge density (in e/nm2)
across the box in z-direction.78,79 These calculations have to be on the graphene walls. For the oppositely charged walls with
performed with suitable boundary conditions.78−80By using the charge density of 1 e/nm2, E0(z) = 18.09 V/nm. In parts a and
Poisson equation b of Figure 12, shown are the electrostatic potential profiles for
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J. Phys. Chem. C 2015, 119, 23955−23967
The Journal of Physical Chemistry C Article

Figure 12. Electrostatic potential profile, Ψ (z) as a function of distance (z) from z = 0 to z = Lz for (a) N2228+/NTf2− and (b) N222(2O2O2)+/NTf2−.
Here Lz is box length (in nm) along the z-direction, Ψ0 is the electrostatic potential due to charged wall, and Ψl is the electrostatic potential due to
ionic liquid. Electric field, E(z) as a function of distance (z) from z = 0 to z = Lz for (c) N2228+/NTf2− and (d) N222(2O2O2)+/NTf2−. Here E0(z) is the
electric field due to charged wall, and El(z) is the electric field due to ionic liquid.

N2228+/NTf2− and N222(2O2O2)+/NTf2− RTILs when confined
between charged and neutral graphene walls. These profiles are
also compared with bare potentials of the applied field. For the
charged walls, the overall potential drop across the box, i.e.
Ψ0(Lz) + Ψl(Lz), for N2228+/NTf2− and N222(2O2O2)+/NTf2− is
7.89 and 11.01 V, respectively. The El(z) profiles in Figure 12,
parts c and d, show oscillatory behavior in the interfacial region
and remain constant in the bulk region for both charged and
neutral walls. Pronounced oscillations in El(z) can be observed
near the charged walls. These oscillatory feature of El(z) near
the walls is due to structural layering of ions at the interface,
(Figure S6) so as to screen the applied field. From parts c and d
of Figure 12 and (Figure S6), we also observe that the electric
field oscillations and overall charge density fluctuations are
larger near the positively charged wall for both the RTILs.
4. CONCLUSIONS
In this study ionic distributions for N2228+/NTf2− and
N222(2O2O2)+/NTf2− RTILs near charged and neutral graphene
23964
sheets have been determined via molecular dynamics
simulations. For the charged graphene, we observe that the
layered structure of the RTILs lasts up to ∼1.5 nm from the
sheets, beyond this length the microscopic structural
organization mimics the corresponding bulk limit. In
corroboration with previous studies, even between the neutral
sheets each system showed layered structure of the RTILs near
the sheets and the layers are composed of both the ionic species
(cation and anion). We observe that the orientation of the
charged species at interface near the charged walls depends on
the charge of the ionic species, charge on graphene sheet, and
chemical nature of the ionic species. We have shown that even
though both perpendicular and parallel tail orientations of
cationic longest tail near the walls exist, parallel orientation of
the tail is preferred for N222(2O2O2)+ system. As shown by
TRDFs and confirmed by isosurfaces, the cation heads (or
anions) in the interfacial region of the negatively (or positively)
charged sheet are more ordered than that in the corresponding
bulk liquids. A natural continuation of this work is to study the
DOI: 10.1021/acs.jpcc.5b06460
J. Phys. Chem. C 2015, 119, 23955−23967
The Journal of Physical Chemistry C
kinetics of charging/discharging and differential capacitance via
MD simulations and their comparison with previously
proposed mean-field theories. We are currently carrying out
such studies on other RTILs to see the effects of cation head
atom modification on ionic distribution in interfacial region and
other electrochemical properties. Further efforts to understand
the effects of cation tail modification with branched or cyclic
alkyl groups81 on the layering pattern of RTILs as well as
mixtures of RTILs with molecular solvents at various kinds of
interfaces are underway.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b06460.
Tables for the box dimensions, LJ parameters, and
supporting figures showing number density profiles,
atomic number density profiles, potential of mean force,
and charge density profiles (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*(H.K.K.) Telephone: +91-(0) 11-26591518. Fax: +91-(0) 11-
26581102. E-mail: hkashyap@chemistry.iitd.ac.in.
Notes
The authors declare no competing financial interest
■
ACKNOWLEDGMENTS
We sincerely thank Professor Ruth Lynden-Bell for helpful
discussions and suggestions while her visit to IIT Delhi. H.K.K.
thanks Professor Ranjit Biswas, Professor Claudio J. Margulis
and Professor Edward W. Castner, Jr. for support and
encouragement. S.S. would like to thank CSIR-UGC, India,
for fellowship. We extend our thanks to CSC, IIT Delhi, for
providing the HPC cluster facility. This work is supported by
the Department of Science and Technology (DST), India,
through a grant awarded to H.K.K. (Grant No. SB/FT/CS-
124/2014).
■
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23967 DOI: 10.1021/acs.jpcc.5b06460

J. Phys. Chem. C 2015, 119, 23955−23967