Article

pubs.acs.org/JPCB

How the Structure of Pyrrolidinium Ionic Liquids Is Susceptible to

High Pressure
Shobha Sharma, Aditya Gupta, and Hemant K. Kashyap*
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India

ABSTRACT: The structural landscape of room-temperature ionic liquids

(RTILs) with longer cationic alkyl tail(s) exhibits polarity ordering (PO)
along with charge ordering (CO). In polarity ordering, which is also
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referred to as intermediate-range ordering, polar groups are separated by

segregated domains of apolar groups and vice versa. Charge ordering
resembles alternation of positive−negative charge groups. In this work,
how these two characteristic orderings respond to applied external
pressure has been investigated via molecular dynamics simulations. The
present study complements the recent experimental studies of Yoshimura
et al. (J. Phys. Chem. B 2015, 119, 8146−8153) and computational studies
of Russina et al. (Phys. Chem. Chem. Phys. 2015, 17, 29496−29500)
wherein the authors described in detail the effects of pressure on the structural and conformational changes in imidazolium based
ionic liquids. Our simulations predict that for 1-alkyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, Pyrr1,n+/NTf2−
with n = 8 and 10, the PO and CO fade when the external pressure increases from ambient pressure to 10000 bar. We observe
that the apolar tail group as well as the polar group correlations are susceptible to the applied pressure. The decrease of polar−
polar and apolar−apolar correlations at higher pressure is accompanied by the enhancement in the polar−apolar correlations and
increased stability/probability of gauche conformations along the cationic tails.

1. INTRODUCTION The pioneering experimental studies of Yoshimura and co-

Stimuli-responsive materials that are capable of making
conformational and/or physiochemical changes on exertion of
external stimuli have gained a wide range of applications in
industry, including biosensing, drug delivery, and separation.1
In the recent past, room-temperature ionic liquids (RTILs)
have found a great deal of attention because of their unique
properties and diverse applications.2,3 RTIL properties can be
fine-tuned by making minor changes in the chemical
composition of their constituent ions. The RTIL response
functions can also be altered by changing the chemical nature of
the ions. In order to conceive RTILs as smart materials, it is
vital to understand how this new class of liquids respond to
external stimuli, such as electric field, temperature, and stress or
pressure. Structural properties of RTILs under ambient
conditions and at elevated temperatures have been thoroughly
examined by experiments4−33 and computer simulation34−49
studies, and these works are nicely summarized and discussed
in the recent review articles.6,50−54 Many RTILs show
anomalous properties when they are subject to electric field55
and temperature.56 However, very little has been addressed
about the pressure-responsiveness of RTILs.52,57−72 Shah and
Maginn studied the structure and dynamics of imidazolium
ionic liquids containing significantly long alkyl chains and
concluded that the thermodynamics and dynamics of these
RTILs could be influenced by pressure.57 Molecular dynamics
(MD) studies done by Zhao et al. on 1-butyl-3-methylimida-
zolium hexafluorophosphate RTIL indicated the deformation of
alkyl chains at higher pressures.61
workers63,67 on the series of imidazolium ionic liquids have
revealed that the ionic liquids could go through structural as
well as conformational changes when the pressure is increased
up to GPa level. The authors also showed that the ionic liquids
could possess multiple phases or render structural transitions at
around 7 GPa.
Recently, Russina et al.70 have reported that, upon increasing
hydrostatic pressure on 1-octyl-3-methylimidazolium tetrafluor-
oborate (Omim+/BF4−), the correlations corresponding to
polar moieties bearing strong electrostatic interactions are
unaffected by the pressure, but the conformations of the alkyl
tails are influenced by pressure. Very much similar to the work
of Margulis73 and Pádua64 on the RTILs with diether
containing cationic tails, the authors claimed that the
enhancement of the gauche conformations along the tail leads
to curling of the cation tail toward the imidazolium ring, and
the overall effect is suppression of PO in the RTIL studied.
According to recent studies, pyrrolidinium cation based
RTILs show more influence of tail modification on their
microscopic properties than the other classes of ionic liquids.74
Cytotoxic studies of ionic liquids have also revealed that these
ionic liquids are less toxic than well-known piperidinium and
imidazolium ionic liquids,74 which makes them more environ-
ment friendly. In the present study, the choice of the 1-alkyl-1-
methylpyrrolidinium bis(trifluoromethylsulfonyl)amide
Received: February 2, 2016
Revised: March 7, 2016
Published: March 9, 2016

© 2016 American Chemical Society 3206 DOI: 10.1021/acs.jpcb.6b01133

J. Phys. Chem. B 2016, 120, 3206−3214
The Journal of Physical Chemistry B
(Pyrr1,n+/NTf2−) ionic liquids with longer tail length stems
from the fact that these liquids show pronounced charge and
polarity orderings under ambient conditions. In these liquids,
the constituent species (cation head, cation tail, and anion) are
structurally complex and can be conformationally excited upon
changing pressure. Several studies on the structure of this class
of ionic liquids have already been pursued.10,38,47,48,73,75,76
However, to the best of our knowledge, only limited studies
have been reported about their response toward a range of
applied pressure. The Margulis and Castner groups have done
comprehensive studies on the structure of RTILs comprising 1-
(cyclohexylmethyl)-1-methylpyrrolidinium, 1-(2-ethylhexyl)-1-
methylpyrrolidinium, and 1-alkyl-1-methylpyrrolidinium cati-
ons paired with bis(trifluoromethylsulfonyl)amide anion via X-
ray scattering experiments and molecular dynamics simula-
tions.47,48,73,75,76 The MD results were in excellent agreement
with the X-ray scattering experiments under ambient
conditions, which allowed the authors to unambiguously assign
the characteristic orderings that to the peaks in total S(q).
Recently, a nice work by Smith and co-workers77 on the
structure of dialkylpyrrolidinium-based RTILs showed that the
RTILs with longer chains could exhibit a structural transition
induced by two-dimensional thin film confinement. The
present work is focused on understanding the structural
responsiveness of 1-alkyl-1-methylpyrrolidinium bis-
(trifluoromethylsulfonyl)amide ionic liquids with increasing
pressure that is isotropically applied to the liquid. Attention is
given on the total and partial X-ray scattering structure
functions along with representative radial distribution functions
(RDFs). The aim of the present work is to know the
susceptibility of charge and polarity orderings to the pressure
increase. The present study also focuses on understanding the
possibility of interdigitation and/or curling of cationic tails
along with conformational changes in the anion at very high
pressure.
2. COMPUTATIONAL DETAILS
All simulations were carried out in the isothermal−isobaric
ensemble using the GROMACS-4.6.5 package.78,79 A total of
3000 ion pairs in a cubic box were used for all the systems
studied. Periodic boundary conditions and minimum image
convention were applied. Nonpolarizable atomistic force-field
parameters from all-atom optimized potentials for liquid
simulations (OPLS-AA)80−83 in conjunction with those of
Lopes and Pádua84,85 (CL&P) were used to model the Pyrr1,n+/
NTf2− RTILs.48,75 The leapfrog algorithm with 1 fs time step
was used for integration of equations of motion. The simulation
boxes for each RTIL were thoroughly equilibrated by raising
and lowering the temperatures, and scaling down the partial
charges. Each system with full atomic charges was allowed to
equilibrate for at least 15 ns at 295 K temperature and at
different pressures (100, 1000, 5000, and 10000 bar) using a
velocity-rescale thermostat and a Parrinello−Rahman86 baro-
stat, respectively. The last 3 ns of the trajectories was saved at
every 100 fs for the computation of the RTIL’s properties. To
get better statistical averages, the properties of the Pyrr1,8+
system were averaged over two independent trajectories. The
cutoff radius for the short-range interactions was set to 1.2 nm.
Electrostatic interactions were evaluated using the Particle
Mesh Ewald (PME)87,88 summation technique with an
interpolation order of 6 and a Fourier grid spacing of 0.08
nm. The equilibrium values of the bulk densities at 295 K for
different pressures are provided in Table 1. A few of the
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Table 1. Simulated Equilibrium Densities (in g/cm3) of the
RTILs at 295 K for Different Pressures
pressure (in bar) Pyrr1,8+/NTf2− Pyrr1,10+/NTf2−
100 1.343 1.301
1000 1.377 1.335
5000 1.467 1.424
10000 1.534 1.488
computed properties at 5000 bar have not been presented here
for clarity. The X-ray scattering static structure function, S(q),
and its ionic and subionic components were computed using
the methodology proposed in the literature.44,48,75,76 The exact
definitions of cation head and tail groups used in this study are
Figure 1. Definitions of the cation (head), cation (tail), and CTS
group in the cation tails. In the CTS group, only carbon atoms are
included.
provided in Figure 1. In brief, the X-ray scattering static
structure function S(q) was computed using eq 1.
S(q) =
n n L /2 sin qr
ρo ∑i = 1 ∑ j = 1 xixj fi (q)f j (q) ∫ 4πr 2[gij(r ) − 1] qr
W (r ) dr
0
n n
[∑i = 1 xi fi (q)][∑ j = 1 xj f j (q)]
(1)
In eq 1, gij(r) is the radial distribution function (RDF) for the
atoms of type i and j. The RDFs include both intra- and
intermolecular pairs. xi is the mole fraction of atoms of type i,
and f i(q) is the X-ray atomic form factor for ith type atoms.89 ρo
= Natom/⟨V⟩ is the total number density, and L is the box
length. W(r) is a Lorch window function defined as W(r) =
sin(2πr/L)/(2πr/L).90,91 The Lorch window function mini-
mizes the effects of finite truncation of r. For a moderately large
system size, the W(r) function has negligible effects on the
physical meaning of the peaks in S(q). To appreciate the
characteristic ordering at different length scales, we used ionic,
subionic, and polarity based partitioning of the total structure
function S(q). Other details of the methodology are described
in the literature.44,75,76 In brief, the total S(q) can be split into
its cationic, Scat−cat(q), anionic, San−an(q), and cationic−anionic,
Scat−an(q) + San−cat(q), subcomponents. The cationic sub-
component can be further decomposed into its head−head,
tail−tail, and head−tail subcomponents, S cat−cat (q) =
Scathead−cathead(q) + Scathead−cattail(q) + Scattail−cathead(q) + Scattail−cattail(q).
Similarly, the cation−anion term can be split into cation head−
anion and cation tail−anion, [Scat−an(q) + San−cat(q)] =
Scathead−an(q) + San−cathead(q) + Scattail−an(q) + San−cattail(q). We can
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group the different terms in the above functions into polar,
apolar, and cross polar−apolar contributions76 as SPolar−Polar(q)
= San−an(q) + Scathead−cathead(q) + Scathead−an(q) + San−cathead(q),
S Apolar−Apolar (q) = S cat tail −cat tail (q), and [S Polar−Apolar (q) +
SApolar−Polar(q)] = Scathead−cattail(q) + Scattail−cathead(q) + Scattail−an(q) +
San−cattail(q).75,76
3. RESULTS AND DISCUSSION
3.1. X-ray Scattering Structure Function, S(q). As can
be seen in Figure 2, the polarity ordering or polar−apolar
Figure 2. Pressure dependence of the simulated total structure
function, S(q), for Pyrr1,8+/NTf2− (upper panel) and Pyrr1,10+/NTf2−
(lower panel) RTILs at 295 K.
alternation peaks that occur below q = 0.5 Å−1 and charge
ordering peaks that occur at around q = 0.7 Å−1 in the X-ray
scattering structure function (SSF) of the Pyrr1,8+ and Pyrr1,10+
systems gradually dim upon increasing pressure. The
appearance of the polarity peaks below q < 0.5 Å−1 and charge
ordering peaks at 0.5 Å−1 < q < 1 Å−1 implies that polarity
ordering occurs at relatively longer characteristic distances than
the charge ordering which occur at shorter length scales but
persists for longer range. Note that these two peaks are also
observed for 1 bar pressure and 295 K temperature (ambient
conditions) and have been reported previously by the Margulis
and Castner groups.48,75,76 Under ambient conditions, the
heights of both PO and CO peaks are more than that for the
lowest pressure studied in this work. Therefore, considering the
previous works48,75,76 and the present study, one can infer that
the two orderings fade when the external pressure increases
from ambient pressure to 10000 bar. While the polarity
ordering peak shows a slight shift toward higher q-values with
increasing pressure, the charge ordering peak shifts toward
lower q-values upon increasing pressure. Also, the polar−apolar
alternation peak almost disappears at the highest pressure,
whereas the charge ordering peak still exists even at very high
pressure. This clearly suggests that the polar−apolar domain
segregation in these liquids has enhanced sensitivity toward the
pressure than the charge ordering. To know the exact origin of
this behavior of these two characteristic peaks (or orderings),
we computed the ionic and subionic components of the X-ray
SSF proposed in the literature.44,48,75,76
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3.2. Charge Ordering. In Figure 3, we have shown cation−
cation, anion−anion, and cation−anion partial X-ray SSFs for
Figure 3. Cation−cation (black line), anion−anion (red line), and
cation−anion (blue line) partial S(q)s of (a) Pyrr1,8+/NTf2− and (b)
Pyrr1,10+/NTf2− RTILs at different pressures.
the Pyrr1,8+ and Pyrr1,10+ systems at different pressures. Peaks
and antipeaks observed at around q = 0.7 Å−1 in these functions
mean that, at the corresponding real-space characteristic
distances, DCO = 2π/qCO, the appreciation or depreciation in
the probability of finding cations (or anions) with respect to
another cation (or anion) are in the same phase44,48,75,76 and
with respect to anion (or cation) are off-phase.44,48,75,76 For
both of the RTILs, the amplitudes of the cation−cation, anion−
anion, and cation−anion partial components gradually decrease
as pressure increases. This means that the charge ordering in
these systems does get diminished or weaker as the pressure
increases. Therefore, the decreased intensity of this peak in the
X-ray SSF at higher pressure is not due to mere cancellations of
the peaks (constructive interference) and antipeaks (destructive
interference). Also, corresponding real-space characteristic
distances, DCO = 2π/qCO, for higher pressure are larger than
those for the lower pressures. This clearly indicates that the
average cation (head)−cation (head), cation (head)−anion,
and anion−anion separations comprising CO are larger at the
higher pressures but the corresponding correlations are weaker.
The weakening of CO at higher pressures is also supported by
the radial distribution functions (RDFs) for the cationic and
anionic nitrogen atoms (Figure 4), namely, Ncat−Nan, Ncat−Ncat,
and Nan−Nan. Clearly, the amplitudes of the peaks correspond-
ing to the nearest solvation shells in all of the RDFs decrease
when the pressure is increased from 100 to 10000 bar, with the
Ncat−Nan RDF being the most sensitive among all three RDFs.
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Figure 4. Ncat−Nan (black line), Ncat−Ncat (blue line), and Nan−Nan
(red line) radial distribution functions for (a) Pyrr1,8+/NTf2− and (b)
Pyrr1,10+/NTf2− RTILs at different pressures.
The susceptibility of subcationic correlations toward pressure
can also be observed for the cation (head)−cation (head),
cation (tail)−cation (tail), and cation (head)−cation (tail)
S(q)s (Figures 5). As already explained by others,48,75,76 cation
heads that are separated by anions contribute to cation
(head)−cation (head) for CO ordering, whereas cation heads
that are separated by the segregated domains of apolar groups
contribute to the cation (head)−cation (head) peak corre-
sponding to PO ordering. It also turns out that the cation
(tail)−cation (tail) correlations have significant contribution to
the PO peak along with cation (head)−cation (head), and both
correlations get weaker upon increasing pressure. To get more
accurate details of charge and polarity orderings, partial X-ray
SSFs for subcationic components (head and tail) with anion
were also computed. From Figure 6, it is clearly visible that,
upon increasing pressure, the amplitudes of both cation
(head)−anion and cation (tail)−anion correlations correspond-
ing to PO and CO peaks are suppressed.
3.3. Polarity Ordering. With regard to the polarity
ordering behavior toward pressure, in Figure 7, we have
shown the polar−polar, polar−apolar, and apolar−apolar partial
X-ray SSFs for both RTILs. In all of the partial components, the
PO peaks at around q = 0.4 Å−1 slightly shift toward larger q-
values (smaller distances) as the pressure is increased. Here the
polar component is comprised of the cation head and anion
and the apolar groups belong to the cation tail (see Figure
1).44,48,75,76 The subcomponents of polar−polar, apolar−apolar,
and polar−apolar X-ray SSFs are provided in Figures 5 and 6.
From these figures, it is obvious that the polar−polar peaks and
polar−apolar antipeaks are also susceptible to the pressure
change along with the apolar−apolar peaks which correspond
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Figure 5. Cation−cation (black line), cation (head)−cation (head)
(red line), cation (tail)−cation (tail) (blue line), and cation (head)−
cation (tail) (green line) partial S(q)s of (a) Pyrr1,8+/NTf2− and (b)
Pyrr1,10+/NTf2− RTILs at different pressures.
to tail−tail correlations. This observation is complemented by
the RDF for the group of three consecutive terminal carbon
atoms, defined as CTS (Figure 1), in the cationic tail at
different pressures, as shown in Figure 8a. The decrease in the
heights of the closest contact peaks, occurring below r = 0.6
nm, in the CTS−CTS RDF as the pressure increases clearly
shows weakening of apolar−apolar correlations. The opposite
trend is observed in the case of cation nitrogen (Ncat) and CTS
correlations with pressure change (see Figure 8b). While the
nearest neighbor Ncat−CTS correlations are enhanced with
increasing pressure, the second solvation shell correlations are
decreased as pressure increases. Moreover, upon increasing
pressure, the distance of closest approach between the tails as
well as Ncat and the CTS group decrease. The adjacency
correlation (AC) peak45,48,75,76 at around q = 1.3 Å−1 in S(q),
which is primarily rendered by close-contact distances between
both cationic and anionic atoms, slightly shifts toward larger q-
values along with decreased intensity with increasing pressure
for both of the RTILs.
3.4. Dihedral Distributions, Cation Tail Curling, and
Anion Conformers. To elucidate on the conformational
aspect of the cation alkyl tails, we computed the probability
distribution function for the number of trans dihedrals along
the alkyl chain of the cations (Figure 9). In agreement with the
previous study,70 the overall probability of finding a greater
number of gauche kinks/defects along the cationic tail is
enhanced as pressure increases. This increase in the number of
gauche kinks in the cationic tails facilitates bending or curling of
the cation tails toward their head groups, which can be clearly
seen in the intramolecular distribution functions for cationic
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Figure 6. Cation−anion (black line), cation (head)−anion (red line), Figure 7. Polar−polar (black line), polar−apolar (red line), and
and cation (tail)−anion (blue line) partial S(q)s of (a) Pyrr1,8+/NTf2− apolar−apolar (blue line) partial S(q)s of (a) Pyrr1,8+/NTf2− and (b)
and (b) Pyrr1,10+/NTf2− RTILs at different pressures. Pyrr1,10+/NTf2− RTILs at different pressures.

nitrogen and the terminal carbon (CTerminal) of the alkyl tail

(Figure 10). We also notice that the probability of finding two
or three trans conformations along the Pyrr1,8+ cation and three
or four along the Pyrr1,10+ cation increases considerably when
the pressure is changed from 1000 to 10000 bar. We also
observe significant broadening of the nearest neighbor peak in
the Ncat−CTerminal intramolecular distribution function at the
highest pressure.
It has been demonstrated previously42,44,63,92 that in liquids
the NTf2− anions exist in equilibrium between two conforma-
tional states about the C−S−S−C pseudodihedral angles, viz.,
gauche or C1 and trans or C2 conformers. The distribution of
intramolecular C−C (carbon−carbon) distance in the anion
also displays two peaks for both of the ionic liquids; the shorter
distance peak resembles the C1 conformer, and the longer C−C
separation peak corresponds to the C2 conformer. Moreover, at
ambient pressure and temperature, the C 2 conformer
dominates. In Figure 11, we show that as the pressure increases
from 100 to 10000 bar the probability of finding C2 conformers
of the anion in both liquids decreases and that of C1 increases.

4. CONCLUSION
In this study, we have used molecular dynamics simulations to
appreciate the structures of Pyrr1,8+/NTf2− and Pyrr1,10+/NTf2−
RTILs at different pressures. The simulated X-ray scattering
structure functions show that the characteristic ordering peaks,
especially charge-ordering and polarity-ordering, in both RTILs
are susceptible to external pressure; the strength of charge-
ordering and polarity-ordering decreases as the applied pressure
increases. Upon increasing pressure, a significant decrease in
3210
Figure 8. (a) Intermolecular RDFs for the CTS group of the cationic
tail for Pyrr1,8+/NTf2− (left panel) and Pyrr1,10+/NTf2− (right panel)
RTILs at different pressures. (b) Intermolecular RDFs for cation
nitrogen and the CTS group of the cationic tail for Pyrr1,8+/NTf2− (left
panel) and Pyrr1,10+/NTf2− (right panel) RTILs at different pressures.
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Figure 9. Probability distribution for the number of trans dihedrals
along the cationic tail. The atoms considered are from the ring
nitrogen through the terminal carbon. In this study, a dihedral angle is
defined as trans when the dihedral angle is within the range 180 ± 20°.
Figure 10. Intramolecular distribution function for the distances
between cationic nitrogen and terminal carbon (CTerminal) of the
longest tail for Pyrr1,8+/NTf2− (left panel) and Pyrr1,10+/NTf2− (right
panel) RTILs at different pressures.
the nearest neighbor pair correlations for both polar−polar and
apolar−apolar groups of the RTILs is also observed. On the
other hand, the polar−apolar nearest neighbor correlations are
stronger at higher pressure. This finding is different from those
observed by Russina et al.70 for Omim+/BF4−, wherein only
apolar moieties are influenced by pressure change. In the
present case, the susceptibility of the polar group correlations
toward the applied pressure could be because of the difference
in the anion and the cation ring; the imidazolium ring and BF4−
have a lower conformational flexibility than the pyrrolidinium
ring and NTf2−. The alkyl tails of cations possess an increased
number of gauche defects at higher pressures than that in lower
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Figure 11. (a) Probability distribution function of C−S−S−C dihedral
angles for NTf2−. (b) Intramolecular distance distribution function for
the carbon atoms of NTf2−.
pressures; this leads to increased bending or curling of the tails
at higher pressure. The probability of finding gauche or C1
conformers of the anion is enhanced at higher pressure, and
that of the trans or C2 conformers is diminished.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: hkashyap@chemistry.iitd.ac.in. Phone: +91-(0)11-
26591518. Fax: +91-(0)11-26581102.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
We sincerely thank Professor Ranjit Biswas, Professor Claudio
J. Margulis, and Professor Edward W. Castner, Jr., for support
and encouragement. S.S. and A.G. thank CSIR-UGC, India, for
a fellowship. We also thank IIT Delhi for providing the
supercomputing 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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J. Phys. Chem. B 2016, 120, 3206−3214