First-principles experimental demonstration of

ferroelectricity in a thermotropic nematic liquid crystal:

Polar domains and striking electro-optics
Xi Chena,b, Eva Korblovab,c, Dengpan Dongb,d, Xiaoyu Weib,d, Renfan Shaoa,b, Leo Radzihovskya,b,
Matthew A. Glasera,b, Joseph E. Maclennana,b, Dmitry Bedrovb,d, David M. Walbab,c, and Noel A. Clarka,b,1
a
Department of Physics, University of Colorado, Boulder, CO 80309; bSoft Materials Research Center, University of Colorado, Boulder, CO 80309;
c
Department of Chemistry, University of Colorado, Boulder, CO 80309; and dDepartment of Materials Science and Engineering, University of Utah, Salt Lake
City, UT 84112

Contributed by Noel A. Clark, April 28, 2020 (sent for review February 19, 2020; reviewed by Nicholas L. Abbott, Peter Palffy-Muhoray, and Pawel Pieranski)

We report the experimental determination of the structure and 5, 16–22). The appearance of polar ordering in these models and
response to applied electric field of the lower-temperature nematic Born’s is considered to be an equilibrium transition between bulk
phase of the previously reported calamitic compound 4-[(4-nitrophe- phases of higher and lower symmetry (23, 24). The models
noxy)carbonyl]phenyl2,4-dimethoxybenzoate (RM734). We exploit its propose order parameters constructed to characterize this
electro-optics to visualize the appearance, in the absence of applied change of symmetry, and provide benchmarks for experimental
field, of a permanent electric polarization density, manifested as a testing, predicting pretransitional behavior as the phase transi-
spontaneously broken symmetry in distinct domains of opposite polar tion is approached from higher or lower temperature, as well as
orientation. Polarization reversal is mediated by field-induced domain describing the properties of the polar ordered phase and its
wall movement, making this phase ferroelectric, a 3D uniaxial nematic distinct symmetry-related states. In the case of relevance here, of
having a spontaneous, reorientable polarization locally parallel to the a uniaxial, nonpolar nematic transitioning to a uniaxial, polar
director. This polarization density saturates at a low temperature nematic with the polarization along the director, there are two

PHYSICS
value of ∼6 μC/cm2, the largest ever measured for a fluid or glassy ordered states related by reflection through a plane normal to
material. This polarization is comparable to that of solid state ferro- the polarization. If such states coexist in a sample, they must
electrics and is close to the average value obtained by assuming per- form reflection-related domains with opposite polarization sep-
fect, polar alignment of molecular dipoles in the nematic. We find a arated by well-defined domain walls (25, 26, 17). Such polar
host of spectacular optical and hydrodynamic effects driven by ultra- domains and their boundaries are also described by the models,
low applied field (E ∼ 1 V/cm), produced by the coupling of the large specifically by the elasticity and order parameter energetics of
polarization to nematic birefringence and flow. Electrostatic self- the polar phase, making the domains the signature features of
interaction of the polarization charge renders the transition from spontaneous polar ordering to be probed and understood in
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the nematic phase mean field-like and weakly first order and controls characterizing the nature of the phase transition. If such domain
the director field structure of the ferroelectric phase. Atomistic mo-
lecular dynamics simulation reveals short-range polar molecular inter- Significance
actions that favor ferroelectric ordering, including a tendency for
head-to-tail association into polar, chain-like assemblies having polar
Conspicuously in the background in the history of liquid crys-
lateral correlations. These results indicate a significant potential for
tals is the ferroelectric nematic (NF) phase. Predicted by Debye
transformative, new nematic physics, chemistry, and applications
and Born 100 y ago and since revisited extensively, in systems
based on the enhanced understanding, development, and exploita-
ranging from colloidal suspensions of rods or discs to melts of
tion of molecular electrostatic interaction.
polar molecules, the existence of the NF has never been certain,
and it has never emerged in interest or applicability from the
liquid crystal | ferroelectric | nematic | polar | liquid shadow of its familiar cousin, the dielectric nematic, the key
component of the displays that enabled the portable comput-

T he first theoretical treatments of collective molecular orien-

tation in liquids, by Debye (1) and Born (2), were electrostatic
versions of the Langevin–Weiss model of the paramagnetic/fer-
ing revolution of the 20th century. Here we show, in a pre-
viously reported thermotropic material, defining evidence for
ferroelectricity and a host of emergent polar behaviors that
romagnetic transition in solids (3). Born envisioned the orienta- promise to remake the science and technology of nematics.
tional ordering of rod-shaped molecules of a nematic as a phase
transition, the proposed ordering mechanism being the interaction Author contributions: X.C., D.D., X.W., M.A.G., D.B., and N.A.C. designed research; X.C.,
of molecular electric dipoles, so that the resulting nematic phase D.D., X.W., R.S., M.A.G., J.E.M., D.B., and N.A.C. performed research; E.K. and D.M.W.
contributed new reagents/analytic tools; X.C., D.D., X.W., L.R., M.A.G., J.E.M., D.B., and
was ferroelectric, i.e., predicted to have a spontaneous nonzero N.A.C. analyzed data; and X.C., J.E.M., D.B., and N.A.C. wrote the paper.
polarization density. Thus, the notion of LCs with polar order, Reviewers: N.L.A., Cornell University; P.P.-M., Kent State University; and P.P., Université
introduced more than a century ago, has grown as a field of broad Paris Sud.
interest and challenge at the frontiers of LC science, stimulating Competing interest statement: D.B. is one of the coowners of Wasatch Molecular Inc.,
rich themes of novel chemistry and physics (4–13) which distributes the APPLE&P database.
However, following Born’s model, some calamitic molecules This open access article is distributed under Creative Commons Attribution License 4.0
without molecular dipoles were found to exhibit nematic phases (CC BY).
(14), while ferroelectricity failed to materialize as a molecular Data deposition: Data, simulations, and videos are publicly available at DOI: 10.17605/osf.
nematic phenomenon. Born’s calculation thus appeared to be io/ZKFTW.
incomplete, stimulating a variety of different models of nematic See online for related content such as Commentaries.
ordering in which both steric and/or electrostatic interactions 1
To whom correspondence may be addressed. Email: [email protected].
were considered. These included the Maier–Saupe theory (15), This article contains supporting information online at https://www.pnas.org/lookup/suppl/
where steric interactions produced apolar (quadrupolar) order, doi:10.1073/pnas.2002290117/-/DCSupplemental.
and others in which the nematic ordering could also be polar (4, First published June 10, 2020.

www.pnas.org/cgi/doi/10.1073/pnas.2002290117 PNAS | June 23, 2020 | vol. 117 | no. 25 | 14021–14031

 boundaries can be moved or removed by application of a field, colinear in these domains in the field-free condition. Increasing
then the mean polarization can be changed, and if this motion is the field causes the domain boundaries to unpin, shrink, and
irreversible, then the polar phase will exhibit switching and hys- disappear (Fig. 1F), moving hysteretically to increase the area of
teresis as emergent properties and can be considered macroscopi- the field-preferred state. The observations of Fig. 1, constituting
cally ferroelectric (27). Here we present the direct observation of a first-principles demonstration of nematic ferroelectricity, are
such spontaneously broken symmetry in the form of domains of
described in more detail below and in SI Appendix, sections S3
opposite polarization, grown without applied electric field, as a first-
principles demonstration of ferroelectricity in a thermotropic, uni- and S4.
axial, nematic liquid crystal (LC) of rod-shaped molecules. Results and Discussion
In 2017, Mandle et al. (28) and Kikuchi et al. (29) separately
reported new LC compounds exhibiting unusual phase behavior: Electro-Optic Observation of Planar-Aligned Cells. Depolarized
two distinct, fluid nematic phases separated in temperature by a transmission light microscopy (DTLM) observations of RM734
weakly first-order phase transition. In both cases, the molecules
were rod-shaped, with several intramolecular dipoles distributed
along their length whose projections onto the molecular long axis
summed to a large overall axial dipole moment of ∼10 Debye.
The high-temperature phase of both mesogens was reported to
be a typical nematic, but they exhibited dramatic paraelectric
(30, 29) and ferroelastic (30) pretransitional effects, with a di-
electric constant surpassing 1,000 as the transition to the low-
temperature phase was approached. The low-temperature phase
exhibited enhanced dipolar molecular associations, reported to
be antiparallel in the Mandle system (28) and suggested to be
parallel in the Kikuchi system, the latter being termed
“ferroelectric-like” (29), giving macroscopic polar ordering in
response to an applied electric field. Mandle et al. subsequently
synthesized a number of homologs of their molecule in an effort
to develop structure–property relationships for this phase (31)
and pursued, in collaboration with the Ljubljana group, a series
of physical studies on one of these (RM734), shown in Fig. 1A,
leading to the claim that this phase was locally polar, as evi-
denced by second harmonic generation, but, on some longer
scale, an antiferroelecric splay nematic (32, 33, 30, 34, 35), a
modulated phase stabilized by local director splay, of the type
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originally proposed by Hinshaw et al. (36).

Our resynthesis of RM734 (SI Appendix, section S1) and ob-
servation of its electro-optic behavior using polarized light mi-
croscopy provides no evidence for a splay nematic phase but
rather leads us to the unambiguous conclusion that upon cooling
from the higher-temperature, nonpolar, uniaxial nematic (N)
phase, RM734 undergoes a transition to another uniaxial ne-
matic (NF) phase that is ferroelectric. The key evidence for this
result is the first observation in a nematic LC of the defining
characteristics of ferroelectricity: 1) the formation, in the ab-
sence of applied electric field, of spontaneously polar domains of
opposite sign of polarization separated by distinct domain Fig. 1. Ferroelectric nematic phase. (A) Structure of RM734 and schematic
boundaries and 2) field-induced polarization reversal mediated of molecular alignment in the ferroelectric nematic (NF) phase. The molec-
by movement of these domain boundaries, as summarized in ular organization is translationally symmetric in 3D and macroscopically
Fig. 1. uniaxial, with local mean molecular long axis, n(r), aligned generally along
In the N phase, the local texture of the planar-aligned cell the buffing direction z, and polar, with a local, mean molecular dipole ori-
shown in Fig. 1 is optically featureless. On cooling toward the NF entation, P(r), along n. H and O are used to represent the methoxy and nitro
phase, a random pattern of stripes extended along the buffing ends of the molecule, respectively. (B–G) DTLM images showing electro-optic
direction appears. Once in the NF phase, these stripes coarsen, evidence for ferroelectricity in a planar-aligned cell of RM734 in the NF phase
(t = 11 μm thick). In the higher-temperature N phase, P(r) = 0, but when
leading to a texture that is again local optically featureless
cooled into the NF phase without an applied field, RM734 spontaneously
(Fig. 1 B–D) but characterized on a larger scale by a pattern of forms macroscopic domains with P > 0 or P < 0. When slowly cooled below
well-defined lines, some delineating distinct, lens-shaped do- the NF phase transition at T = 133 °C, the initial texture (B) coarsens into a
mains 100 μm or more in extent (Fig. 1 D–G), all formed in the pattern of domains with distinct boundaries (C). (D–G) T = 120 °C. Starting
absence of applied electric field. Application of an ultrasmall from D with no field, application of an ultrasmall in-plane test field |Ez|
(∼1 V/cm), in-plane, DC test field, E, applied along z, parallel to ∼0.5 V/cm along the buffing direction produces reversible reorientation of P
the in-plane buffing and therefore to the director n(r), shows that without changing its magnitude. (E and F) Application of a negative Ez starts
for E > 0 the director inside these domains begins to reorient, the in-plane reorientation of n(r) about x inside the domains, producing the
while the orientation outside remains fixed (Fig. 1E), whereas for dark bands there, while (G) positive Ez produces reorientation outside of the
domains, proving that these regions are of opposite polarization. The E ∼
E < 0 the region outside the lens-shaped domains reorients, and
1 V/cm threshold field for this reorientation indicates that n(r) in these do-
the orientation inside remains fixed (Fig. 1G), indicating that the mains is coupled to E by a polarization P ∼5 μC/cm2, which is comparable to
domain boundaries separate regions with opposite response to the bulk polarization density measured electronically. The higher applied
in-plane field and therefore of opposite in-plane polarization. field in F has moved the boundary of one lenticular domain to increase the
The lack of response to increasing E outside of the lenses in area with the field-preferred orientation, effecting a hysteretic reversal of
Fig. 1E and inside the lens in Fig. 1G shows that P and n are P(r). (Scale bar, 30 μm.)

14022 | www.pnas.org/cgi/doi/10.1073/pnas.2002290117 Chen et al.

 were made principally in cells with a t = 11-μm-wide gap between
the glass plates, one of which was coated with a pair of planar
ITO electrodes uniformly spaced by d = 1.04 mm, which enabled
application of an in-plane electric field, E, between them, largely
parallel to the cell plane (y, z). The plates were treated with a
polyimide layer buffed in the z direction, normal to the electrode
edges, so that the applied field was along the buffing direction: E =
zE (SI Appendix, Fig. S3). The cells were filled by capillarity with the
LC in the isotropic phase. Both the N and NF phases were studied,
with results as follows.

Nematic Phase. When cooled into the nematic (N) phase, RM734
formed textures with the nematic director, n(r), the local mean
molecular long axis and the optic axis, parallel to the plates Fig. 2. DTLM images showing polar Freedericksz twist transition in ferro-
(planar alignment). The white-light birefringence color at T = electric domains with opposite polar orientation at T = 120 °C. These do-
140 °C was a uniform pale yellow-orange, in the third-order mains, grown field-free upon cooling from the N phase to this temperature,
Michel–Levy band (retardance ∼ 1,500 nm) (37), with the have a polarization density P. (A) Field-free initial state showing three do-
mains separated by domain walls, each domain having n(r) along the buffing
larger index for optical polarization along n. The azimuthal
direction z. (B) Application of an ultra-small, positive test field Ez = 1 V/cm
orientation of n(r) was generally along z but with a fixed pattern induces a birefringence color change resulting from in-plane reorientation
of in-plane orientational defects and weak, continuous variations of n(r) in the center domain, leaving the upper and lower domains un-
of the in-plane orientation, as seen in SI Appendix, Figs. S4 and changed. (C) Application of Ez < 0 induces an in-plane reorientation of n(r) in
S6A, suggestive of a relatively weak coupling to the azimuthal the upper and lower domains. There is little optical change or reorientation
anisotropy of the surface. Measurements give a uniaxial bi- in the central domain. If the field is returned to E = 0, the system returns to
refringence Δn ∼ 0.2 (SI Appendix, Fig. S17), suggesting that the the starting state (A). These observations demonstrate that the domains are
polar and also enable the absolute determination of the direction of P(r):
alignment is planar, with n(r) nearly parallel to the plane of the
domains that have the orientation preferred by the applied field do not
plates. Tilting the cell away from being normal to the light beam

PHYSICS
reorient. In this experiment, P(r) and n(r) within the domains rotate about x
did not reveal significant tilt of n(r) out of the cell plane, but a but the field is not large enough to move the domain walls, which are
small (few-degree) pretilt may be present. In addition to the pinned by the surfaces. The polarization vectors (shaded green) and circular
locally uniform, planar texture imposed by the surfaces upon arcs (white) depict the field-induced reorientation of P(r) in the midplane of
cooling into the N phase, we observed a few twisted areas (SI the cell: P(r) does not reorient at the surfaces in this experiment, remaining
Appendix, Fig. S6A), but generally, the local preferred orienta- parallel to the buffing direction. These field-induced reorientations with P(r)
tion was the same on the two plates and therefore likely estab- starting nearly antiparallel to E are polar azimuthal Freedericksz transitions.
The threshold field, EP = (π/t)2(KT/P), estimated using the measured P ∼5 μC/
lished by a combination of the buffing with surface memory (38) cm2 at T =120 °C (Fig. 3), is EP ∼1 V/cm, comparable to the fields employed
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of the nematic director pattern as it was first growing out of the here. t = 11 μm. (Scale bar, 30 μm.)
isotropic.

Ferroelectric Nematic Phase. Upon cooling through the N–NF either nearly parallel to or antiparallel to z. In the domains where
transition, the cell becomes patterned with a texture of irregular P is nearly antiparallel to E, the polarization responds by rotating
domains extended locally parallel to n(r), first appearing on a toward E. The optical response to test fields makes the differ-
submicron scale but then annealing over a roughly 2 °C interval ence in polarity readily distinguishable, leaving no doubt that
into patterns of elongated lines of low optical contrast (Fig. 1B) these domains are polar. The green vectors in Fig. 2 indicate the
that are also oriented generally along n(r). Some lines coarsen field-induced reorientation of P(r) in the midplane of the cell.
and extend along n, while others form closed loops, 10 to 200 Tilting of the cell shows that this reorientation is azimuthal [φ(r)]
microns in extent, having a distinctive characteristic lens shape, about x, with n(r) remaining parallel to the (y, z) plane.
elongated along n(r) (Fig. 1 C and D). Sample textures from this In an applied electric field, the n(r) field of the preferred
evolution are shown in Fig. 1, with additional images in SI Ap- states becomes only slightly better aligned along the field di-
pendix, Figs. S4–S9. Upon completion of the transition, apart rection, evidence that n and P are parallel. We considered the
from these loops, the texture is smooth and very similar to that of possibility that the NF phase is biaxial, with n along z and sec-
the N phase at high T (SI Appendix, Fig. S6). A small increase of ondary directors oriented preferentially parallel and normal to
Δn is observed at the transition (SI Appendix, Fig. S17), and Δn the cell surfaces. When such a biaxial phase grows in from a
then increases continuously with decreasing temperature, T, higher-temperature uniaxial phase, the cell generally exhibits
behavior in agreement with that previously reported for the arrays of characteristic disclination lines where 180° flips of the
nematic order parameter (33). secondary directors have become trapped at one or both surfaces
The NF phase exhibits striking electro-optic behavior in (39). If such structures were present in our cells, they would show
DTLM, starting with the response to the application of tiny up clearly in the polarized light microscope, but none are ob-
(<1 V/cm) in-plane electric fields. This sensitivity was exploited served. We conclude that the bulk NF condition is uniaxial, with
to probe and understand the static and dynamic changes of n(r) n parallel to P in the absence of applied field. When an electric
and P(r) in applied electric fields. Typical textures observed in field is applied, n(r) experiences electric torques through its
these experiments, and the responses used to identify ferro- coupling with P, which we assume remains substantially locally
electric domains and determine their polarization orientation, parallel to n, i.e., that the local optic axis is parallel to P.
are indicated in Fig. 2. In the absence of applied field, the LC SI Appendix, Fig. S4, shows a larger area of the t = 11 μm cell
director n in these cells is generally along the buffing direction z, in orientations having the average director along the crossed
and we observe domains separated by distinct boundaries. As in polarizer/analyzer direction (SI Appendix, Fig. S4 A and F–H)
Fig. 1, one set of domains responds only weakly to fields applied and at 45° to it (SI Appendix, Fig. S4 B–E), illustrating that the
along z, indicating that in these regions, P is already parallel to E overall textural alignment gives reasonably good extinction be-
and therefore that before the field is applied, P is everywhere tween crossed polarizers but with some brighter regions allowed

Chen et al. PNAS | June 23, 2020 | vol. 117 | no. 25 | 14023
 because of the softness of the anchoring as noted above. The P ∼ 6 μC/cm2, a value comparable to the ∼4 μC/cm2 found by
images show polarization reversal driven by an adjustable DC in- Kikuchi et al. in the compound DIO (29). Polarization in the
plane electric field. The textures of n(r) in the limiting states of N–NF transition temperature region may include pretransitional
plus or minus E are identically black but separated by a striking contributions in the N phase due to the divergence of e‖ (30), but
sequence of domain wall formation, coarsening, and disappear- this has not yet been studied in detail. The estimate above of P
ance, all in the weak DC field range −2 V/cm < E < 2 V/cm. The from the polar twist threshold EP at T = 120 °C agrees well with
field-aligned states extinguish between crossed polarizers as in SI the P data in Fig. 3, indicating that the magnitude of spontane-
Appendix, Fig. S4A, meaning that that they have n(r) everywhere ous polarization achieved field-free in domains grown and
parallel to z, and show a pink birefringence color in the third- cooled from the N phase is comparable to that induced by a field
order Michel-Levy band as in SI Appendix, Fig. S4B. The in- in the NF phase, as expected for a ferroelectric.
termediate states have n(r) in the (y, z) plane but with spatial Further significance of P ∼ 6 μC/cm2 can be appreciated by
variation of its azimuthal orientation φ(r) about x. This lowers calculating a polarization estimate Pe = p/v, where p = 11 Debye is
the effective retardance of these regions, moving their bi- the axial molecular dipole moment of RM734 (31) (SI Appendix,
refringence down into the second- and first-order Michel–Levy sections S9 and S10) and v is the volume/molecule in the phase,
bands and producing intense birefringence colors. The uniformly v = 325 cm3/mole = 540 Å3/molecule, assuming a LC mass density
oriented domains obtained following field reversal are states in of ρ = 1.3 g/cm3 (SI Appendix, sections S9 and 10). Using these
which the n, P couple has been reoriented in the bulk LC and parameter values and assuming complete polar ordering of the
also flipped on the aligning surfaces, the latter mediated by molecular long axes, we find Pe ∼ 6.8 μC/cm2, comparable to our
domain wall motion. measured P at low T and indicating that RM734 has extremely
The field-induced reorientations in the planar-aligned geom- strong spontaneous macroscopic polar ordering, a condition
etry of Figs. 1 and 2 are twist deformations of the azimuthal impossible in any state with domains of competing polarization
orientation of n(r) about x, having the form φ(r) = φc(x) cos(πx/t) as in the proposed splay nematic, for example. This value of P is
for small φc, where φc(x) is the reorientation pattern in the cell confirmed by our atomistic molecular dynamics (MD) simula-
midplane. This deformation can be generated in a uniaxial di- tions, which yield P ∼ 6.2 μC/cm2 in an equilibrated simulation
electric N phase using an in-plane AC electric field to induce a of 384 molecules polar ordered in the NF phase, as discussed
twist Freedericksz transition, for which the threshold field will be below and in SI Appendix, sections S9 and S10. This P value is
given by ED = (π/t)√(K/eoΔe) (40). Assuming a cell gap t = roughly six times larger than the highest polarization ever
11 μm, typical nematic values of Frank elastic constant K ∼ 5 pN, achieved in tilted calamitic or bent-core chiral smectic LCs (42,
and a dielectric anisotropy Δe ∼ 5, one finds ED ∼ 1,000 V/cm, 43), is comparable to that found in polar columnar phases (44),
giving an estimate which sets the field scale for typical in-plane and is well within the range exhibited by solid-state oxide (45)
dielectric nematic electro-optics. The fields required to produce and organic (46) ferroelectrics. This result, combined with our
the reorientations in the NF phase in Figs. 1 and 2 are three textural observations, indicates that the NF phase is a three-
orders of magnitude smaller. In small applied fields, electrical dimensional (3D), fluid, macroscopically homogeneous, polar
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torque on the director field τE = P × E comes from the coupling uniaxial nematic phase. The agreement with the spontaneous P
of field to polarization. With this polar coupling and P(x) starting measured from the polar twist threshold indicates that this is
antiparallel to E, our observed field-induced reorientations are the ferroelectric state.
polar Freedericksz transitions for which the torque balance Given these very large polarization values, we summarize here
equation is KTφxx + PEsinφ(x) = 0, where KT is the twist elastic and detail in SI Appendix, section S2, several of the relevant
constant (41, 40). This gives a field threshold of EP = (π/t)2(KT/P) features of high-polarization electro-optic, electrostatic, and
and a cell midplane reorientation of φc(E) ≃ √[6(E − EP)/EP], elastic behaviors developed in the study of chiral smectic ferro-
so that a φc = 0 to φc = 90° reorientation occurs in the field range electric LCs, which can now be expected for the NF, some of
EP < E0–90 < 1.4 EP. Measurements of E0–90 yield an experi- which are reported here. These include the following: 1) One
mental value of the threshold of EP ∼ 1 V/cm, from which we can feature is polar twist Freedericksz transition (Fig. 1 and SI Ap-
estimate P. Taking KT to be in the range 2 pN < KT < 5 pN gives pendix, Fig. S5). 2) A second feature is boundary penetration
a value for P in the range 3 μC/cm2 K P K 6 μC/cm2. (47). The polar coupling to field limits the distance in which
We also measured P(T) directly from the field-induced cur- boundary- or defect-preferred orientations transition into bulk
rent associated with polarization reversal. We used both square- field-preferred orientations. This penetration length ξE = √K/PE ∼
and triangle-wave driving fields in several different, two-terminal 1 μm for P = 6 μC/cm2 and an applied field E = 1 V∕cm (Fig. 4). 3)
cell geometries, including an in-plane cell similar to that used for A third feature is block polarization reorientation and expulsion of
the electro-optics but with gold electrodes (SI Appendix, Fig. S3) splay (splay-elastic stiffening) (48–55). A second self-penetration
100-μm-thick sandwich cells with conventional gold electrodes length, ξP = √eK/P2 ∼ 0.1 nm, is the scale above which the po-
and a 0.5-mm diameter, cylindrical capillary with the LC in a larization field can spontaneously expel spatial variation of orien-
150-μm gap between planar electrode faces oriented normal to tation [∇·P(r) = −ρP] that produces space charge, ρP. The result is
the cylinder axis (SI Appendix, Fig. S3). Time integration of the that low-energy elastic distortions of the n, P couple are bend or
current signals obtained using these geometries produced con- twist only, with splay of n(r) and P(r) expelled from the bulk and
sistent values of the polarization density as a function of tem- confined to narrow reorientation walls, as in Fig. 5 A and B and SI
perature. Typical polarization data obtained from the in-plane Appendix, Fig. S4. The resulting polarization blocks can effectively
cell using a square-wave drive frequency f = 200 Hz are shown in screen applied field, producing, for example, the large threshold
Fig. 3. The cell current showed only small capacitive and resistive field required for the splay–bend Freedericksz transition in the NF
contributions in the N phase but, upon cooling into the NF phase, phase (SI Appendix, section S6). 4) A fourth feature is field-induced
became dominated by an additional peak which exhibited the torques proportional to E. The balance of field-induced torque
characteristics of ferroelectric LC polarization current, carrying a proportional to PE with viscous torques gives a characteristic
driving amplitude-independent net charge Q (from which P was reorientation risetime on the order of τ = γ1/PE, where γ1 is the
calculated) and exhibiting a risetime τ varying inversely as the nematic rotational viscosity (41, 56). The risetime τ = γ1/PE is
drive amplitude (Fig. 3C). The resulting P increases continuously ∼0.1Δt, where Δt is the reversal time (Fig. 3C), giving a value of γ1
from small values at the transition, saturating at low T at a value ∼ 0.1 Pa s, comparable to that of 5CB at T =25 °C. 5) The N–NF

14024 | www.pnas.org/cgi/doi/10.1073/pnas.2002290117 Chen et al.

 phase transition is strongly affected by the polarization self-
interaction, which suppresses the longitudinal modulation δPz of
P (50), producing the strong anisotropy of the polarization fluctu-
ations in the N phase and rendering the transition mean-field (SI
Appendix, section S3).
The electro-optic response of the NF phase in a cell with an
electric field applied in-plane shows uniquely polar features, with
P(r) reorienting in the (y, z) plane through an azimuthal angle
φ(r) about x determined by the local surface, elastic, and electric
torques. Buffed surfaces stabilize two planar-aligned states (φ=0
and φ=π) with opposite signs of P(r), so the cell has four stable
states, two that are uniform and two that are twisted, illustrated
in Fig. 4. These equilibrium states are separated by π surface
disclination walls (magenta dots in the section drawing of Fig. 4).
If complete polarization reversal is to be achieved by an applied
field, P must be switched on both surfaces. We refer to domain
boundaries such as these, where both n and P reorient but
maintain a fixed relative sign, as polarization-director (P-n)
disclinations (PnDs). If the vectorial representation n(r) is used
to describe the nematic texture, then with only PnDs the local
orientation of P(r) relative to n(r) will be either parallel or an-
tiparallel everywhere. In Fig. 4, an applied field preferring the
uniform (U) dark state is deforming a central (magenta) domain
that had polarization that was initially opposed to the field and is
now partially rotated toward it (green vectors). This central
domain forms a twisted–untwisted (TU) state in which the di-

PHYSICS
rector twists along x from the surface-preferred alignment par-
allel to z at one cell plate through azimuthal angle φ(x) to the
field-aligned orientation in the midplane of the cell and then
twists back to the surface-preferred alignment on the other glass
plate. The field causes the central domain to shrink, moving and
eventually eliminating the disclination walls in order to achieve
complete polarization reversal. The motion of the walls on the
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two cell surfaces is different because the pinning strengths are

different and spatially inhomogeneous, with the result that they
do not remain in register, leading to the formation of the (olive)
left- and (gold) right-handed twisted states TL and TR seen
surrounding the central domain in Fig. 4 A and B. The color of
the central TU domain (green, blue, or pink in Fig. 4C) varies
with the degree of field-induced reorientation of n, P in the
sample midplane.
Several other modes of field-induced polarization reversal are
shown in Fig. 5 and SI Appendix, Fig. S4. The initial response of a
uniformly aligned region to an increasing in-plane DC field in
the range 0 < E < 2 V/cm that opposes the local polarization is to

material reoriented by the applied field. In the NF phase, the polarization

reversal current becomes a distinct peak that grows in area on cooling, in-
dicative of an increasing polarization density, and the reorientation takes
place more slowly, reflecting the increase of orientational viscosity. The
double-headed arrow shows the reversal time at T = 110 °C (dashed drop
lines in C). (B) The polarization density P of RM734 measured on cooling
(black squares) saturates at P ∼6 μC/cm2 at the lowest temperatures. The
open circles are values of P of the plupolar nematic calculated from the
POL MD simulation of the NF phase (Fig. 7 and SI Appendix, Sections S9
and S10). In the plupolar nematic, long-wavelength orientation fluctuations
are suppressed, giving a P value determined by molecular-scale fluctuations
and local packing. RM734 approaches the plupolar condition at low T. The
region near the transition has not been studied in detail. (C) Field depen-
Fig. 3. Characteristics of polarization reversal in an applied field. (A) Tem- dence of the reversal time Δt, taken as the full width at half-height of the
perature dependence of the cell current with a 200-Hz square wave gen- polarization or optical reversal pulse following a field step in a 100-Hz, bi-
erating a field Ep = 95 V/mm applied in-plane to a t = 15-μm-thick cell with polar, square-pulse train of peak amplitude Ep in planar-aligned cells with in-
1-cm-wide ITO electrodes spaced by d = 1 mm. In the I and N phases (T ≥ plane electrodes spaced by d = 20 μm, 60 μm, and 1 mm at T = 110 °C. The
133 °C), the current is small and capacitive. On cooling into the NF phase, an reversal time scales as 1/Ep as expected for reorientation driven by ferroelec-
additional current contribution appears, the area of which is independent of tric torques. The dashed lines identify the measurement with Ep = 95 V/mm
voltage and is equal to the net polarization reversal charge, Q = 2PA, where highlighted in A. The risetime τ = γ1/PE is ∼0.1Δt, giving a value of γ1 ∼0.1 Pa-
A = 15 μm × 1 cm is the effective cross-sectional area of the volume of LC s, comparable to the viscosity of 5CB at T =25 °C.

Chen et al. PNAS | June 23, 2020 | vol. 117 | no. 25 | 14025
 shows snapshots during field reversals generated by a 5-Hz AC
triangle wave voltage with different amplitudes. As the field
amplitude increases from 0 to Ep = 10 V/cm, the stripes become
very regular and narrowly spaced. The herringbone pattern of
polarization in the stripes gives an overall structure where Pz is
constant, ensuring that there is no net polarization charge at the
stripe boundaries, and where the backflow induced in each stripe
matches that of its neighbor. The field is not strong enough to
reverse the surfaces in this case. A different reorientation mode
is illustrated in Fig. 5B, where field reversal leads to the for-
mation of polygonal domains in which charge-stabilized areas of
uniform P are bounded by sharp domain boundaries, each ori-
ented along a vector l such that P·l has the same value on either
side of the boundary, as shown in panel 4. As with the stripes
above, this geometry reduces the net polarization charge on the
line. Similar structures are found in high-P chiral smectic fer-
roelectrics (57) and in ferromagnets (58). The textures of the
charge-stabilized domains can also be employed to visualize di-
rectly the reorientation of P(r) under applied field, as shown in
Fig. 5C, where a circular air bubble enables tracking of the polar
orientation of n(r) during field reversal. The director is anchored
tangent to the bubble surface, resulting in a director field that is
largely bent around the bubble, with splay concentrated in two
180° wedge disclinations (red dots). n(r) in the area surrounding
the bubble is parallel to the line connecting these defects. The
n(r), P(r) structures observed with increasing reversal field
strength are sketched below each panel.

Nematic Ferroelectrohydrodynamics. The polarization density of

the NF phase creates a fluid which is extraordinarily responsive
both to external applied fields and to internally generated po-
Fig. 4. DTLM images of a large, twisted domain with surface polarization larization space charge. While the discussion above has focused
on the effects of field-induced molecular reorientation, the most
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pointing to the right, surrounded by a uniform region with surface and bulk
polarization pointing to the left, in the direction of an applied field. (A) interesting and useful effects of the NF may be its ferroelec-
Twisted domain (magenta) and structural elements P, n, and E. (B) The trohydrodynamic or ferroelectrorheological behavior, exempli-
section drawing shows the two-dimensional structure of the cell in the x, z
fied by the observations shown in Fig. 6 and SI Appendix, section
plane along the top edge of the image: the uniform (U), field-preferred state
of the background; the surface orientations reversing at the boundaries of S7. In this experiment, RM734 is filled into a t = 10 μm cell with
the central domain; P in the twisted–untwisted (TU) state in the center of the random-planar alignment of n. An in-plane electric field is ap-
domain, with the orientation in the middle of the cell indicated by green plied using a pair of gold electrodes evaporated with a d = 60 μm
vectors, and the intermediate left- and right-handed twisted states TL and TR gap onto one glass plate, visible at the bottom of Fig. 6A. A
(olive and gold). π surface disclination lines (magenta dots) mediate polari- square wave voltage with Vp = 5 V applied between the elec-
zation reorientation at the top (pink line) and bottom (cyan line) cell plates.
trodes generates an electric field distribution where E(r) is uni-
Where the surface disclination lines overlap, the director is uniformly ori-
ented along y through the thickness of the cell, giving extinction between
form in the electrode gap and in the surrounding area is directed
the crossed polarizers (dark spots circled in A). In the absence of applied along half-circular arcs centered on the gap (SI Appendix, Fig.
field, the left and right surface polarization states are energetically equiv- S15 A, Inset). In the NF phase, this field induces flow of localized
alent. (C) The central domain shrinks with increasing E field. The bi- defects (Fig. 6B) and their surrounding fluid with a velocity field
refringence color changes from green to blue to pink as the rotation of P in v(r,t) locally parallel to E(r) and changing direction with the
the middle of the cell increases. T = 120 °C. t = 11 μm. Silica spheres (orange
field, suggesting an electric body force density F(r) = ρ(r)E(r),
arrow) for visual size reference in the bottom of C have an apparent di-
ameter of 4 μm (See SI Appendix, Fig. S10). (Scale bars, 35 μm.)
where ρ(r) is a positive electric charge density. When E(r) goes
through E = 0 during field reversal, flow ceases, and the director
field breaks up into P-reversal bend-domain bands like those
shown in Fig. 5A as it rotates alternately through +π and −π,
form a zigzag modulation in the orientation of n(r) and P(r),
giving the radial texture seen in Fig. 6A. Thus, dynamically P(r,t)
illustrated in SI Appendix, Fig. S4, in which the nonzero spatial
is everywhere parallel to E(r,t) and v(r,t) when voltage is applied.
variation is ∂n(r)/∂z, along the director, making it a bend wave. The fact that the product P(r)·E(r) is unchanged by applied field
Bend has a lower polarization space charge energy cost than a reversal and yet v(r) changes sign indicates that ρ(r) does not
splay wave (which, with nonzero ∂n(r)/∂x, would generate stripes change sign with P(r), i.e., that the driving has caused the fluid to
parallel to n rather than normal to it). As the field strength is become charged. The structure of polarization reversal bands in
increased, the degree of reorientation increases, and distinct the neighborhood of the electrode gap is shown in detail in SI
boundaries appear between the half-periods of the modulation, Appendix, Fig. S16.
separating stripes of uniform internal orientation. Fields of a few We measured vp, the initial value of the defect velocity upon
V/cm drive complete (+π, −π, +π, −π) reorientation of n in the field reversal at the location indicated in Fig. 6A. This velocity
cell midplane, at which point these boundaries become 2π walls depends dramatically on temperature, as shown in Fig. 6C, with
suboptical in resolution, ∼ξP in width. This process is even more flow being essentially absent in the N phase and commencing
dramatic with dynamic driving, as illustrated in Fig. 5A, which upon cooling through the N–N F transition. The velocity

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 PHYSICS
Fig. 5. Common polarization reversal scenarios in RM734. Field-induced reorientation of P is indicated schematically using white arcs and green vectors. (A)
Stripe formation. Applying a 5-Hz triangle-wave electric field with peak amplitudes in the range 0 < Ep < 10 V/cm to a region with an initially uniform in-plane
director (panel 1) induces a periodic modulation in the orientation of n(r) and P(r) along z (a director bend wave; panel 2) whenever the field changes sign. As
the applied field strength is increased (panels 3 and 4), the stripes form with sharper boundaries and have uniform internal orientation determined by the
field strength. The zigzag arrangement of the director in successive stripes ensures that the normal component of P is constant across the stripe boundaries, so
that there is no net polarization charge there. (B) Polygonal domains. During field reversal, polarization charge effects alternatively lead to the formation of
tile-like domains with uniform n(r). These polygons have sharp domain boundaries that are oriented such that P·l, where l is along the boundary, is the same
on both sides of the boundary, reducing space charge. The angular jump in n(r) across the boundary highlighted in panel 4 is 90°. (C) Director field reor-
ientation around inclusions. Air bubbles in the cell can be used to track the orientation of n(r) in a reversing field. The director field near the bubble, sketched
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below each panel, is locally distorted, bending around the inclusion with splay deformations confined to two 180° wedge disclinations (red dots) located at
opposite ends of the bubble. The blue color in panels 4 and 5 is indicative of a TU state of the kind shown in Fig. 4, with a surface disclination then moving out
from the bubble boundary to give the final, uniform state seen in panel 6. (Scale bars, 40 μm in A, 30 μm in B, and 20 μm in C.)

eventually decreases with decreasing T, presumably because of Under these circumstances, accumulation of one sign of charge
the increasing viscosity of the LC. in the fluid can occur when an applied AC field gets out of phase
The experiments show that applied electric field promotes the with polarization reversal. Additional inherent asymmetries,
creation of regions with positive charge density. Charging of the such as differences in mobility or chemical character between
NF by AC applied fields is to be expected due to the bulk polarity positive and negative ionic impurities, or an intrinsic tendency
of the phase. Electrode surfaces contact NF material where the for splay distortion of the P(r) field itself, can also contribute.
direction of P alternates in time. The NF, because of its polar
symmetry, has diode-like, polarity-dependent resistance that can Atomistic MD Simulation
also depend on the sign and nature of the charge carrier. The We carried out MD simulations directed toward gaining an un-
bulk charge mobility along z in the NF phase may also depend on derstanding of how features of molecular architecture, interac-
field direction. Beyond this, there will be a variety of charging tions, and correlations are related to the polar ordering of the NF
effects due to the linear coupling of P and flow. Let us consider, phase. These calculations used a simulation box containing 384
for example, steady, incompressible nematic laminar flow; then RM734 molecules (SI Appendix, Fig. S18) with periodic bound-
the director is generally nearly parallel to the velocity, and v(r) = ary conditions, equilibrated in the NPT ensemble at P = 1 atm
v(r)n(r). Since ∇·v(r) = 0 we have ∇·n(s) = [ln v(s)]/∂s, where s is for a range of temperatures spanning the N and NF phases, using
the position variable along the flow: where the velocity increases, the APPLE&P force field (59) successfully applied in previous
the director splays inward. However, in the NF phase we have studies of nematic (60) and twist-bend (61) phases. More details
P(r) = Pn(r), where P is the constant polarization magnitude, so of the simulations can be found in SI Appendix, sections S9
that laminar flow produces polarization charge density ρP(s) = and S10.
−P∇·n(s) = −P∂[ln v(s)]/∂s, the sign of which depends on The simulations probe the equilibration of RM734 in two
whether P is aligned along v or opposed to it. Complex flows will distinct condensed LC states: 1) polar (POL), a polar nematic
thus produce complex patterns of polarization charge. Reor- state generated by equilibrating a starting condition that is per-
ientation of P generates displacement current, J = ∂P/∂t, which is fectly ordered in the +z direction of the polar molecular long-
locally normal to P(r) and, if driven by electric field, gives a axis vectors u, which point from the nitro (O) to the methyl (H)
highly anisotropic contribution to the net electrical conductivity, end of each molecule as seen in Fig. 7A, and 2) nonpolar
σ⊥ = P2/γ1 for E ⊥ P, and σ|| = 0 for E || P (43). For RM734, we (NONPOL), a weakly polar, nematic state generated by equili-
obtain σ⊥ ∼10−3/Ωcm, which is in the semiconducting range. brating a starting condition with no net polar order (50%/50%

Chen et al. PNAS | June 23, 2020 | vol. 117 | no. 25 | 14027
 fluctuations as well as diffusive molecular motion. Their equili-
brated states are distinct, however: the steric packing of the
anisotropic molecules makes head-to-tail molecular flipping
events extremely rare during the simulation space–time volumes,
so the equilibrations obtained have an effective constraint of no
molecular flipping.
These POL and NONPOL states represent the extremes of
equilibrated polar order and polar disorder in the simulation
volume. Limiting the simulations to these states, i.e., not con-
sidering molecular flips in a simulation of polar order, may seem
like a significant shortcoming. However, when we use the POL
state to calculate P, we obtain polarization densities that match
those of RM734 at low T (Fig. 3B), implying that at low tem-
peratures the ordering of RM734 becomes that of the simulated
POL state, making this an ideal model system for exploration of
the molecular correlations leading to polar order.
The positional pair-correlation functions, gP(ρ, z) and gNP(ρ, z),
of the equilibrated POL and NONPOL systems are shown in
Fig. 7 B–E, where for the NONPOL system, gNP(ρ, z) = gNPpar(ρ, z) +
gNPanti(ρ, z) is the sum of the correlations between the molec-
ular pairs with relative parallel or antiparallel orientations of u.
The g(ρ, z) are φ-averaged conditional probability densities of
molecular centers around a molecule with its center at the origin
and long axis along z and thus are uniaxially symmetric in (ρ, φ, z)
cylindrical coordinates, reflecting the uniaxial symmetry of the N
and NF phases. They all exhibit a molecule-shaped, low-density
region [g(ρ, z) ∼ 0] around the origin resulting from the steric
overlap exclusion of the molecules, an asymptotic constant density
at large ρ, and distinct peaks indicating preferred modes of mo-
lecular packing. The normalized average density is <g(ρ,z)> = 1. If
we were to consider a similarly equilibrated system of rods marked
O and H on their ends but which were otherwise symmetric (e.g.,
hard spherocylinders marked as either OH or HO) then both of the
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orientational states would have identical pair-correlation functions,

gP(ρ, z) = gNP(ρ, z) = 2gNPpar(ρ, z) = 2gNPanti(ρ, z). The g(ρ, z) of
RM734, in contrast, show a number of striking differences that
directly exhibit the effects of its structural and electrostatic polarity
on the packing of neighboring molecules.
The POL gP(ρ, z) in Fig. 7B shows the equilibrated, local
Fig. 6. Field-induced flow in the ferroelectric nematic phase. (A) DTLM image molecular packing preference in the limit of polar order, i.e., in
of a t = 10-μm-thick, planar-aligned cell of RM734 between untreated glass the system with the maximum number of contacts between like-
plates, in the NF phase at T = 120 °C. The black bars at the bottom are two
evaporated gold electrodes on one of the plates, separated by a d = 60 μm
oriented molecules. Its prominent features are sharp, on-axis
gap. The electrodes are outlined in white for clarity. Only the upper edges of arcs at (ρ = 0, z = ±22 Å), indicating on-average coaxial mo-
the electrodes and the adjacent part of the cell are shown. A square-wave lecular association into polar chain-like (OH–OH–OH) associ-
voltage with Vp = 3 V, 0.1 Hz, is applied to the electrodes, producing an electric ations having a center-to-center spacing along z of the molecular
field in the plane of the cell. This field drives a pattern of defect motion and length, 22 Å, stabilized by the electrostatic attraction of the nitro
fluid flow over the entire field of view, with the defect velocity v(r) (white and methoxy ends of the molecules (Fig. 7F), and off-axis peaks
arrows) parallel to the applied field, E(r) (green), which is tangent to half- at ρ = 5 Å, z = ±6 Å, indicating polar side-by-side association
circles centered on the electrode gap (SI Appendix, Fig. S12). Where the de-
fects are dense, their motion transports the surrounding fluid. When the field
(Fig. 7G). These correlations indicate that specific electrostatic
is applied, the entire region shown here moves along the field lines. This im- interactions between oppositely charged groups on the two
age, captured during field reversal, shows a periodic array of bend domain molecules (e.g., between positively charged terminal or lateral
walls normal to the director (yellow) and the applied field, as in Fig. 5A, in this methoxy H atoms and negatively charged nitro O atoms) play a
case along radial lines. (B) Typical defect in the texture moving along the dominant role in stabilizing such pair configurations.
applied field direction (down in Left and up in Right), in the location circled in The NONPOL system enforces the maximum number of mo-
A. (C) Temperature dependence of the magnitude of the initial defect velocity
lecular contacts between molecules of opposite orientation. In this
along the white dashed track in A following a field reversal. There is no flow in
the N phase but on cooling into the NF phase, the velocity increases rapidly
situation of maximum polar disorder, possible equilibrated mo-
with increasing P before decreasing again at lower T because of the increasing lecular correlations could range from being 1) dominantly anti-
viscosity. A similar dependence on T is observed whether heating or cooling. parallel end-to-end [e.g., OH–HO–OH chains, with side-to-side
(Scale bars, 1 mm in A and 100 μm in B.) polar correlations, as in the bilayer smectics of strongly polar
molecules (62)] to being 2) polar end-to-end (a mixture of OH–
OH–OH and HO–HO–HO chains with the OH–HO interactions
division of the u vectors along +z/−z). Each molecule can then side by side). RM734 is distinctly in the latter category as, re-
be labeled as OH or HO, depending on its orientation (whether markably, the principal polar ordering motifs of Fig. 7 F and G are
u is along +z or −z, respectively). Equilibration with respect to even stronger in the NONPOL system than in the POL (compare
the internal molecular arrangements of these two systems is Fig. 7 B and D), and the antipolar correlations are largely side by
readily achieved through orientational and internal molecular side. The OH–HO end-to-end antipolar association depicted in

14028 | www.pnas.org/cgi/doi/10.1073/pnas.2002290117 Chen et al.

 PHYSICS
Fig. 7. Results of atomistic molecular dynamic simulations probing molecular-scale organization leading to polar order. (A) RM734, showing its geometrical
long axis vector u, terminating at the nitro- (O) and methoxy (H) molecular ends. A nanoscale volume containing 384 molecules is equilibrated into two
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distinct LC states: a POLAR system with all polar molecular long axes, u, along +z and a NONPOLAR system with half along +z and half along −z. Equilibration
of the molecular conformation and packing is readily achieved, but end-to-end flips are rare, so the simulated states remain in the polar or nonpolar limit of
equilibrated nematic order. (B–E) Molecular positional/orientational pair correlation functions: conditional probabilities of molecular centers (magenta),
about centers fixed at the origin (white dots). (B, F, and G) The POL simulation shows directly the dominant pair correlations adopted by molecules that are
polar ordered, in the form of conditional probability densities, g(ρ,z), of molecular centers (magenta fill) around a molecule with its center (white dots) at the
origin and long axis u along z. The g(ρ,z) are φ-averaged to be uniaxially symmetric, reflecting the uniaxial symmetry of the N and NF phases. They exhibit a
molecule-shaped, low-density region [g(ρ,z) ∼0] around the origin resulting from the steric overlap exclusion of the molecules; an asymptotic constant value
at large ρ giving the normalized average density [g(ρ,z) = 1]; and distinct peaks indicating preferred modes of molecular packing. This analysis reveals two
principal preferred packing modes in the POL system: (B and F) polar head-to-tail association stabilized by the attraction of the terminal nitro and methoxy
groups and (B and G) polar side-by-side association governed by group charges along the molecule, nitro-lateral methoxy attraction, and steric interactions of
the lateral methoxys. (D and E) The NONPOL system exhibits distinct correlation functions for antiparallel and parallel molecular pairs, gNPanti(ρ,z) and
gNPpar(ρ,z). (E, H, and I) The preferred antiparallel packing gives strong side-by-side correlations, governed by group charges along the molecule, and (E, J, and
K) weaker antipolar nitro–nitro end-to-end association. (D, F, and G) The parallel correlations in the NONPOL system are the most relevant to the stability of
polar order in the NF phase as they are determined by the inherent tendency of the molecular interactions for polar ordering in the presence of enforced
polar disorder. Comparison of B and D shows identical preferred modes of parallel association in the two systems, with the POL system correlations being even
stronger in the NONPOL system. This is clear evidence that the polar packing motifs giving the correlation functions (B) and (D), exemplified by the sample
POL MD configurations (F) and (G), stabilize the polar order of the ferroelectric nematic phase.

Fig. 7J is present but weak, as is the HO–OH end-to-end pairing of polar ordering yielding the simulated P values shown in Fig. 3
Fig. 7K. The latter is dominant in the crystal phase (32) but not as a (open circles). Comparing these polarization values with the
mode of achieving antipolar ordering in the NONPOL system. It RM734 data shows 1) that in the plupolar state, the fluctuations
appears from these results that the polar correlations identified in that lead to the phase transition are clearly suppressed, while the
the POL system, and persisting in the NONPOL system in the remnant short-range fluctuations give a P value exhibiting only a
maximal presence of enforced polar disorder, must be those re- weak dependence on temperature, and 2) that this P gives a good
sponsible for stabilizing the NF phase. account of the polarization density of the NF at low temperature,
The POL simulation equilibrates a state in which end-to-end evidence that at low T the NF phase approaches a comparable
flipping is kinetically arrested and the periodic boundary condi- plupolar-like condition where there are only short-range fluctua-
tions suppress long-wavelength orientation fluctuations (λx > tions and where the simulated g(ρ, z) faithfully represent their
55 Å and λz > 70 Å). The remnant short-ranged fluctuations lead correlations.
to pair correlations which, as we have shown in Fig. 7, are con-
fined to the volume ρ <10 Å and z < 30 Å about the origin, Materials and Methods
molecular neighbor separation scales which are well within the Synthesis of RM734. 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethox-
dimensions of the simulation box. These conditions create a ybenzoate (RM734; Fig. 1A) is a rod-shaped mesogen first synthesized by
“plupolar” [plus quam polar (63)] equilibrium state of constrained Mandle et al. (31). It was reported to have an isotropic (I) phase and two

Chen et al. PNAS | June 23, 2020 | vol. 117 | no. 25 | 14029
 additional phases with nematic character, with transition temperatures as Polarization measurements were made by using transimpedance electronics
follows: I–187 °C–N–133 °C–NX–X. Our preparation is based on general syn- to integrate the current in response to an applied electric field, using several
thetic reactions and uses procedures only slightly modified from those de- in-plane geometries and a glass capillary cell with coaxial electrodes (SI
scribed in the literature cited (SI Appendix, section S1). Appendix, section S1).

Observations of Response to Applied Electric Field. Experimental cells were Data Availability. Data, simulations, and videos are publicly available at DOI:
made by filling LC samples between glass plates coated with lithographically 10.17605/osf.io/ZKFTW.
patterned ITO or gold electrodes and spaced to a desired gap, t. Both
transparent capacitor and in-plane electrode geometries were employed. ACKNOWLEDGMENTS. This work was supported by Materials Research
Experiments were performed in temperature-controlled environments, with Science and Engineering Center Grant DMR 1420736 and by NSF Condensed
electro-optic observations carried out using DTLM with cells mounted on the Matter Physics Grant DMR 1710711. L.R. was supported by a Simons
rotary stage of a research microscope and imaged in transmitted light be- Investigator Award from the Simons Foundation. We also acknowledge
tween polarizers. The sign and magnitude of the in-plane birefringence the Center for High Performance Computing at the University of Utah for
were determined using a Berek compensator (SI Appendix, Fig. S17). allocation of computing resources.

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