Journal of Molecular Liquids 333 (2021) 116039

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Dynamic spreading of a water nanodroplet on a nanostructured surface

in the presence of an electric field
Ben-Xi Zhang, Shuo-Lin Wang, Xin He, Yan-Ru Yang, Xiao-Dong Wang ⇑
State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, North China Electric Power University, Beijing 102206, China
Research Center of Engineering Thermophysics, North China Electric Power University, Beijing 102206, China

a r t i c l e i n f o a b s t r a c t

Article history: Molecular dynamics simulations are implemented to investigate the statics and dynamics of wetting for a
Received 19 January 2021 water nanodroplet on a nanostructured surface in the presence of a vertical electric field. The results
Revised 25 March 2021 show that the electric field induces electro-stretching, electro-wettability, modified solid-liquid interfa-
Accepted 30 March 2021
cial tension, and pinning at the triple line, and they jointly affect the spreading exponent and static con-
Available online 6 April 2021
tact angle of the nanodroplet. Under an upward electric field, the spreading is always hindered, and the
static contact angle monotonously increases with the field strength. Interestingly, under a downward
Keywords:
electric field, the spreading is first hindered and then is promoted as increasing the field strength, leading
Polar water molecules
Electro-wettability
to a first increased and then decreased static contact angle. The increased solid-liquid interfacial tension
Electro-stretching and the enhanced pinning are found to be two main mechanisms for the slowing down of spreading and
Pinning the increase in static contact angles for both electric fields at low field strengths. The same trends are
Hydrogen bonds observed at high field strengths under the upward electric field; however, exactly the reverse trends
occur under the downward electric field, leading to the acceleration of spreading and the decrease in sta-
tic contact angle at high field strengths. Moreover, it is found that the enhancement in intrinsic wettabil-
ity of the surface can suppress the breaking of hydrogen bonds, thereby reducing the solid-liquid
interfacial tension and accelerating the spreading. The enhancement in intrinsic wettability can also
reduce the pinning at the triple line as well as the energy barrier of the Cassie-Wenzel transition, which
contributes to the reduced static contact angle.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction adsorption and desorption events of liquid molecules on solid sur-

Dynamic wetting occurs when a droplet spreads over a solid
surface, which is of great significance in many practical applica-
tions, such as inkjet printing, surface coating, boiling, and conden-
sation [1]. Two kinds of classical models, hydrodynamics (HD)
models [2] and molecular kinetic theory (MKT) models [3], have
been proposed to interpreted the spreading kinetics of droplets
on solid surfaces. Within the framework of HD models, the
dynamic wetting is driven by capillary force or gravitational force,
and is resisted by viscous force. Depending on the driving force, the
spreading obeys a scaling law of r ~ t1/10 in the capillary regime and
r ~ t1/8 in the gravitational regime [4–6]. However, within the
framework of MKT models, the dynamic wetting is attributed to
⇑ Corresponding author at: State Key Laboratory of Alternate Electrical Power
System with Renewable Energy Sources, North China Electric Power University,
Beijing 102206, China.
E-mail address: wangxd99@gmail.com (X.-D. Wang).
faces, and hence, follows a different scaling law of r ~ t1/7 [7–9].
With the development of surface fabrication technologies [10],
various textured surfaces with nano/microstructures are widely
employed to manipulate dynamic wetting behaviors of droplets.
On such surfaces, droplets can suspend on or collapse into nano/
microstructures, forming to the Cassie or Wenzel state [11,12].
Because the size of macrodroplets is serval orders of magnitude
larger than the characteristic size of nano/microstructures, nano/
microstructures only modify the surface wettability. However, for
nanodroplets, the droplet size is comparable to the characteristic
size of nanostructures, so that nanostructures not only change
the surface wettability but also may cause a significantly enhanced
pinning effect. This enhanced effect is recently confirmed by an
analysis of the local atomic density in the vicinity the triple line
[13]. Thus, an extra energy dissipation is generated by the local
pinning effect, leading to the distinctly different spreading kinetics
of nanodroplets on nanostructured surfaces. Zong et al. [14] inves-
tigated the spreading of water nanodroplets on hydrophilic nanos-
tructured surfaces. They found that because of the strong pinning

https://doi.org/10.1016/j.molliq.2021.116039
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al.
effect, the movement of water molecules is much more directional
on nanostructured surfaces than that on smooth surfaces. The
directional movement causes an extra dissipation in the bulk liq-
uid, hindering spreading. Yuan et al [15] demonstrated that when
a nanodroplet spreads over a hydrophilic textured surface with
flexible nanopillars, the liquid is accelerated by nanopillars when
approaching nanopillars but is pinned when passing nanopillars.
Owing to these two effects, the spreading obeys a scaling law of
r ~ t1/3 in the early stage, whereas the spreading exponent
decreases in the late stage because the pinning force gradually
becomes dominant as the nanodroplet are impaled on more
nanopillars. These two effects are also found on hydrophilic nanos-
tructured surfaces with rigid nanopillars, and hence, the scaling
law of r ~ t1/3 occurs again on such surfaces [16]. The nanogrooves
between nanopillars provide an additional driving force to acceler-
ate the infiltration of suspended liquid. On the other hand, nanopil-
lars also bring extra resistance to the movement of collapsed
liquid. The competition between the two opposite effects affects
the advancing and receding of the triple line as well as the static
apparent contact angle of nanodroplets. As a result, a reasonable
design of nanostructures is very important for the manipulation
of dynamic wetting of nanodroplets.
In parallel with nanostructures, applying an external electric
field to nanodroplets is also a feasible approach to manipulate nan-
odroplets because the electric field can modify the static contact
angle of nanodroplets. For macrodroplet, the modified contact
angle is described by the Lippmann-Young equation,
coshe = coshY+(ere0V2)/2dclv, where he is the static contact angle
when voltage V is applied, hY is the Young contact angle, clv is
the liquid-vapor interfacial tension, d is the electric double layer
thickness, er is the dielectric constant of the insulator layer, and
e0 is the permittivity of vacuum [17]. However, this equation can-
not describe the static contact angle of nanodroplets in the pres-
ence of electric fields because there is a scale effect for
electrowetting of nanodroplets. The electric double layer that can
shield the electric field hardly forms for nanodroplets, and hence,
nanodroplets are more sensitive to the electric field than macro-
droplets [18–22]. Furthermore, the enhanced electric field effect
also causes a direction-dependent static contact angle of nan-
odroplets. Zong et al. [23] presented that for a water nanodroplet
spreading over a smooth surface subjected to a vertical electric
field, the solid-liquid interfacial tension decreases in the presence
of an upward electric field, whereas it increases when a downward
electric field is applied. As a result, a larger static contact angle is
observed for the water nanodroplet under the downward electric
field when the field strength remains unchanged. Song et al. [24]
investigated the spreading of a nanodroplet on a smooth surface
subjected to a horizontal electric field. They found asymmetric sta-
tic contact angles on two sides of the nanodroplet. The asymmetry
first increases and then decreases with the field strength, and
finally disappears when the field strength exceeds a critical value.
This interesting phenomenon is explained by a combined
interaction of electro-wettability, electro-stretching, and inter-
molecular forces.
Recently, several studies also paid their attention to the spread-
ing of a nanodroplet over a nanostructured surface in the presence
of an electric field. Zhao et al. [25] demonstrated that as the field
strength increases, a suspended nanodroplet eventually collapses
into a superhydrophobic nanostructured surface, corresponding
to a wetting transition from the Cassie state to the Wenzel state.
Yen et al. [26] reported that for a nanodroplet in the Cassie state
subjected to a vertical electric field, the small solid-liquid contact
area weakens the electro-wettability effect, so that the electro-
stretching effect becomes dominant, which lifts up the droplet
and increases the static contact angle as compared with that in
the absence of the electric field; however, for a nanodroplet in
2
Journal of Molecular Liquids 333 (2021) 116039
the Wenzel state, the electro-wettability and pinning effects
dominate over the electro-stretching effect, leading to a decreased
static contact angle.
There are electro-wettability, electro-stretching, and pinning
effects on nanostructured surfaces, and they jointly affect the stat-
ics and dynamics of wetting of nanodroplets. However, the under-
lying mechanism remains poorly understood. In this work, MD
simulation are implemented to study the statics and dynamics of
wetting of nanodroplets on a nanostructured surface in the pres-
ence of a vertical electric field. The field strength, field direction,
and intrinsic wettability of the surface are altered in simulations
to reveal the effects of electro-wettability, electro-stretching, and
pinning.
2. Simulation method
2.1. Interaction potentials
The spreading of a water nanodroplet on a gold nanostructured
surface is studied. The simple- point charge/extension (SPC/E)
model is employed to characterize the properties of water mole-
cules, which is kept rigid by the SHAKE algorithm [27]. This model
was also employed in previous studies of nanodroplets in the pres-
ence of an external electric field [28–30]. The interactions between
water molecules consist of the Lennard-Jones (L-J) 12-6 and
Coulombic potentials, expressed as,
"
12
6 #
rij rij qi qj
U ij ¼ 4eij  þ ð1Þ
r ij r ij r ij
where Uij is the pair potential between the ith and jth atoms, rij is
the distance between the ith and jth atoms, eij and rij are the energy
and distance parameters, and qi and qj are the charges of the ith and
jth atoms.
A gold (100) nanostructured substrate is constructed by face-
centered cubic (FCC) crystals, in which the gold atoms in the bot-
tom three layers are fixed to prevent the substrate deformation.
The interactions between gold atoms are described by the embed-
ded atom method potential, expressed as,
X 1XX  
Ei ¼ F i ðqi Þ þ / r ij ð2Þ
i
2 i j–i ij
where Ei is the energy of ith atom, Fi is the embedding energy that is
a function of the atomic electron density qi, and /ij is a pair poten-
tial. There are three main force field parameters, a, b, and t, for the
Au-Au interactions, which are taken from Ref. [31] and listed in
Table 1. The interactions between water molecules and gold atoms
are modeled by the L-J 12-6 potential. The intrinsic wettability is
associated with the interactions between liquid and solid, the
strong solid-liquid interactions can enhance the intrinsic wettabil-
ity. On the basis of such a fact, the intrinsic wettability is adjusted
by altering the energy parameter eO-Au, as shown in Table 1.
2.2. Simulated system
Fig. 1 shows the schematic of the simulated system, which is a
cuboid box with dimensions of 57 nm (x)  1.6 nm (y)  80 nm (z).
The boundary condition applied to the box is periodic in the x- and
y- directions, whereas it is fixed in the z-direction, with a reflect
wall being assigned to the top of the box. When atoms collide with
the reflect wall, they will bounce back to the box without the loss
of kinetic energy. In the present simulations, a two-dimensional
cylindrical droplet is adopted to save the computational cost.
Although the cylindrical droplet is nonexistent in the nature, the
study of its spreading is still of great importance to understand
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al. Journal of Molecular Liquids 333 (2021) 116039

Table 1
Values of the potential parameters employed in the present simulations.

Particles i j ri,j (Å) eij (eV) qe (eV) h (°) a b t

O-O 3.1660 0.0068 0.8476 — — — —
H-H 0.0000 0.0000 +0.4238 — — — —
O-H 0.0000 0.0000 — — — — —
O-Au 2.8675 0.0214 — 60.0 — — —
O-Au 2.8675 0.0266 — 47.0 — — —
O-Au 2.8675 0.0312 — 42.0 — — —
O-Au 2.8675 0.0340 — 32.0 — — —
H-Au 0.0000 0.0000 — — — — —
Au-Au — — — — 1.4475 0.1269 2

Fig. 1. The initial configuration of the simulated system. Gold atoms are yellow, oxygen atoms are blue, and hydrogen atoms are pink.

to real spreading processes. This is because cylindrical and
spherical droplets follows the same spreading law. A water nan-
odroplet with radius of R0 = 45 Å (3500 water molecules) and a
gold substrate (23496 gold atoms) decorated with nanogrooves
are mounted in the box. The thickness of the cylindrical nan-
odroplet is taken as 16 Å based on the requirement of periodic
boundary conditions. The gold substrate has a thickness of 24 Å,
and the nanogrooves in the gold substrate have a constant aspect
ratio of h/w = 1 (height h = 1.2 nm and width w = 1.2 nm).
The water nanodroplet and gold substrate are respectively
relaxed in the NVT ensemble at 298 K to reach equilibrium. After
that, a uniform electric field in the z-direction is applied to the sys-
3
tem, so that an additional force fe,i = qiE is exerted on each charged
atom. After the initial configuration is constructed, simulations are
implemented using the LAMMPS (large-scale atomic/molecular
massively parallel simulator). The PPPM (particle-particle
particle-mesh) method is employed to solve the long-range elec-
trostatic interactions with an accuracy of 10-4 [32], and the
velocity-Verlet algorithm is employed to solve the Newtonian
motion equations of particles at a time step of t = 1 fs [33]. The con-
tact angle and spreading radius are calculated based on a free-
surface fitting method. The nanodroplet above the nanogrooves
is divided into many layers with a layer thickness of 3 Å. The num-
ber density of water molecules in each layer is calculated as a func-
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al.
tion of the distance from the center of mass of the layer. The radius
R(t) in each layer is determined by the number density, namely
98% of water molecules in the layer are contained. The profile of
the nanodroplet is fitted by the radius in each layer, and the con-
tact angle is calculated by the fitted profile.
3. Results and discussion
3.1. Electrowetting of nanodroplet on nanostructured surface
Simulations are first implemented with the following fixed con-
ditions to understand the statics and dynamics of electrowetting
on nanostructured surfaces. The aspect ratio of nanogrooves is h/
w = 1, and the intrinsic wettability of the nanostructured surface
is h0 = 60°, corresponding to the energy parameter of eO-
Au = 0.0214 eV. A downward electric field with field strength of
E = 0.05 V Å1 is applied to the nanodroplet. Fig. 2 presents the
snapshots of a water nanodroplet spreading over the nanostruc-
tured surface. As shown in Fig. 2(a), when no electric field is
applied, the bottom liquid first infiltrates nanogrooves to form a
composite surface composed of nanopillars and collapsed liquid,
whereas the bulk liquid remains nearly stationary until three
nanogrooves are infiltrated by the collapsed liquid at t = 70 ps. It
should be noted that although the nanodroplet is in the Wenzel
state, it still remains nearly spherical. Subsequently, accompanied
with the further infiltration, the bulk liquid starts to spread over
the composite surface, and the droplet evolves into a hemisphere.
Finally, when six nanogrooves are fully infiltrated, the spreading
stops and the nanodroplet has a static contact angle of he = 53°.
However, as shown in Fig. 2(b), in the presence of the electric field,
the bottom liquid fills up three nanogrooves at t = 60 ps, and the
nanodroplet evolves into an ellipsoid instead of the sphere in the
absence of the electric field. When the nanodroplet reaches equi-
librium, only five nanogrooves are fully infiltrated, leading a larger
static contact angle of he = 67°.
Hydrogen and oxygen atoms have different electronegativity
values, and hence, water molecules are polar with a partial positive
charge for each hydrogen atom and a partial negative charge for
each oxygen atom. Water molecules can be approximately consid-
ered as point dipoles because of their small sizes. In the absence of
an external electric field, point dipoles are randomly oriented
owing to thermal motions, so that the nanodroplet shape is gov-
erned only by interfacial tensions, as shown in Fig. 2(a). However,
when an electric field is applied to the nanodroplet, electric field
forces make point dipoles reorient themselves. Under the down-
ward electric field, the reorientation leads to positively charged
(a)
0 ps 26 ps 70 ps
(b)
0 ps 30 ps 60 ps
Fig. 2. Morphology evolution of a water nanodroplet on a nanostructured surface: (a) in the absence of an electric field and (b) in the presence of a downward electric field
with field strength of E = 0.05 V Å1.
Journal of Molecular Liquids 333 (2021) 116039
hydrogen atoms facing towards the gold surface but negatively
charged oxygen atoms against the surface [24]. Owing to this
directional arrangement of water molecules, the nanodroplet
would be elongated along the field direction, which is referred to
as an electro-stretching effect [34,35]. Thus, the nanodroplet shape
is controlled by both electro-stretching and interfacial tensions,
forming an ellipsoid in the early stage of spreading, as shown in
Fig. 2(b). Because only a small field strength of E = 0.05 V Å1
is employed in this case, the electro-stretching effect is relatively
weak, and hence, the droplet finally evolves into a hemisphere,
as the same as that in the absence of the electric field.
Besides the electro-stretching effect, applying an external elec-
tric field to nanodroplets also produces an electro-wettability
effect. The directional arrangement of water molecules caused by
electric fields may break hydrogen bonds formed between water
molecules [24]. The bond breaking promotes the migration of
water molecules to liquid and solid surfaces because they are no
longer constrained by hydrogen bonds. As a consequence of the
migration, water molecules more readily infiltrate nanogrooves
and wet solid surfaces, which is referred to as the electro-
wettability effect [36]. It is worth noting that the static contact
angle of the nanodroplet subjected to the electric field is larger
than that in the absence of the electric field. This result is com-
pletely opposite to that of macrodroplets, indicating that the
electro-stretching effect outweighs the electro-wettability effect.
The force balance in the horizontal direction at the triple line
can be expressed as clvcoshe = Few + Fc-Fp [37], where Few is the
electro-wettability force, Fc = csv-csl is the capillary force, Fp is
the pinning force, csv is the solid-gas interfacial tension, and csl is
the solid-liquid interfacial tension. In general, the pinning force
can be ignored for macrodroplets when the droplet size is much
larger than the microstructure size, so that the equation is reduced
to clvcoshe = Few + Fc, which can be considered as a variant of the
classical Young-Lippmann equation. However, the pinning effect
becomes significantly strong and hence cannot be ignored for nan-
odroplets. Daub et al. [22] presented that the solid-liquid interfa-
cial tension for nanodroplets can be related to the average
number of hydrogen bonds per molecule, and a larger hydrogen
bond number means a lower solid-liquid interfacial tension.
Fig. 3 shows the average number of hydrogen bonds, <nHB>, per
water molecule in the vicinity of the solid-liquid interface. The fol-
lowing three conditions are used to distinguish whether a hydro-
gen bond forms between two water molecules. First, the
distance, RO-O, between the oxygen atoms of two water molecules
is smaller than the critical one, RO-O,c. Second, the distance, RO-H,
between the hydrogen atom accepting a lone pair of electrons
and the oxygen atom donating a lone pair of electrons is less than
170 ps 512 ps 1666 ps 2000 ps
202 ps 524 ps 1574 ps 2000 ps
4
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al. Journal of Molecular Liquids 333 (2021) 116039

3.20 Downward Applying an electric field also affects the dynamics of spreading
Upward [41–44]. The evolution of spreading radius for the water nan-
3.18
odroplet with or without an electric field is shown in Fig. 5. The
3.16 spreading can be divided into two stages. In an early spreading
3.14 stage, the spreading is not affected by the electric field, whereas
the spreading is deaccelerated in the later spreading stage when
<nHB>

3.12
a downward electric field is applied to the droplet.
3.10
3.08 3.2. Effect of field strength
3.06
3.04 The effect of field strength on the statics and dynamics of wet-
ting for a water nanodroplet on a nanostructured surface is inves-
3.02
tigated under the following conditions. The nanogrooves have an
0 0.03 0.05 0.07 0.09 aspect ratio of h/w = 1 and intrinsic wettability of h0 = 60°. A down-
ward electric field is applied to the nanodroplet with field
E (V Å-1) strengths of E = 0.03, 0.05, 0.07, and 0.09 V Å1. Figs. 2
and 6 show the snapshots of the nanodroplet with and without
Fig. 3. Average number of hydrogen bonds per water molecule in the vicinity of the
solid-liquid interface in the presence of an upward or a downward electric field. the electric field during spreading. When no electric field is
applied, six nanogrooves are eventually infiltrated by the collapsed
liquid; however, there are only five for the field strengths of
the critical one, RO-H,c. Third, the OOH bond angle, /, is less than a
E = 0.03, 0.05, and 0.07 V Å1. Interestingly, when the field
critical one, /c. The values of the critical parameter are taken as RO-
strength further increases to E = 0.09 V Å1, the number of infil-
O,c = 3.6 Å, RO-H,c = 2.4 Å and /c = 30° [26]. The thickness of water
trated nanogrooves increases to six, as the same as that in the
molecular layer is 5 Å, which is larger than the hydrogen bond
absence of the electric field.
length of 2.8 Å. As shown in Fig. 3, <nHB> significantly decreases
Fig. 7 shows the static contact angle as a function of field
at the field strength of E = 0.05 V Å1, as compared with that in
strength for the water nanodroplet on the nanostructured surface
the absence of the electric field. Therefore, the solid-liquid interfa-
in the presence of a downward electric field. To verify the reliabil-
cial tension increases, which leads to a reduced Fc and hence an
ity of data, the static contact angles of droplets with radii of R0 = 30
increased static contact angle.
and 51 Å in the presence of a downward electric field are also sim-
The pinning effect hinders the movement of the triple line,
ulated and drawn in Fig. 7. The data show good agreement for the
which makes water molecules accumulate in the vicinity of the tri-
three nanodroplets. As expected, the static contact angle increases
ple line, thereby leading to a high local density of water molecules.
when the field strength changes from E = 0 to 0.05 V Å1. How-
Fig. 4 shows the number density of water molecules in the vicinity
ever, an abnormal result occurs when further increasing the down-
of the triple line with and without an electric field. Here, the sim-
ward field strength. The static contact angle starts to decreases
ulation box is divided into multiple small cells with dimensions of
when the field strength varies from E = 0.05 to 0.09 V Å1.
0.3 nm (x)  0.3 nm (z), the number density in each cell is calcu-
The static contact angle is 35.5° at E = 0.09 V Å1, which
lated. A significantly higher number density is observed at E = 0
decreases by 18° as compared with that in the absence of the elec-
.05 V Å1 than that in the absence of the electric field, which agrees
tric field.
with the previous reports [24,38]. The increased number density
Because the mechanisms for static contact angles at low down-
provides evidence for the enhanced pinning effect, which was also
ward field strengths have been discussed in Section 3.1, only the
experimentally reported by Ren et al. [39] and Baviere et al. [40].
abnormal variation of static contact angles at high field strengths
Therefore, the enhancement of pinning effect is another reason
are analyzed here. As shown in Fig. 3, the average number of
for the increased static contact angle of nanodroplets on nanos-
hydrogen bonds per water molecule in the vicinity of the solid-
tructured surfaces when an external electric field is applied.
liquid interface increases when the downward field strength is lar-
ger than 0.05 V Å1, which causes a reduced solid-liquid interfacial

Downward
14 100
Upward
90
80
12 70
60
50
(N Å-3 )

10
40
R (Å)

8
30
E= 0 V Å-1
6
20 E= -0.03 V Å-1
E= -0.05 V Å-1
4 E= -0.07 V Å-1
E= -0.09 V Å-1
0 0.03 0.05 0.07 0.09
10
0.1 1 4
E (V Å ) -1

t (ns)
Fig. 4. The number density of water molecules in the vicinity of the triple line on
the nanostructured surface in the presence of an upward or a downward electric Fig. 5. Evolution of spreading radius of a water nanodroplet on a nanostructured
field. surface in the presence of a downward electric field.

5
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al. Journal of Molecular Liquids 333 (2021) 116039

(a)

0 ps 32 ps 70 ps 122 ps 220 ps 1418 ps 2000 ps

(b)

0 ps 30 ps 60 ps 310 ps 344 ps 1320 ps 2000 ps

(c)

0 ps 30 ps 60 ps 322 ps 404 ps 1052 ps 2000 ps

Fig. 6. Morphology evolution of a water nanodroplet on a nanostructured surface in the presence of a downward electric field at: (a) E = 0.03 V Å1; (b) E = 0.07 V Å1; and
(c) E = 0.09 V Å1.

90 2.0
E= 0 VÅ
-1
30 Å Downward
1.8 E = -0.03 V Å
-1

80 45 Å Downward
E = -0.05 V Å
-1
51 Å Downward 1.6
E = -0.07 V Å
-1

70 45 Å Upward 1.4
substrate

E = -0.09 V Å
-1

1.2
θ (°)

-3

60
NÅ

1.0

50 0.8
0.6
40 0.4
0.2
30
0.0
0 0.03 0.05 0.07 0.09 0 20 40 60 80 100 120 140 160

Z (Å )
3
E (V Å-1)
Fig. 8. The number density of water molecules in the z-direction in the presence of
Fig. 7. The static contact angle as a function of field strength in the presence of an
a downward electric field.
upward or a downward electric field.

increase in field strength, namely it first decreases and then

tension and hence an increased capillary force Fc. Thus, the
decreased static contact angle for the downward field strength lar-
ger than 0.05 V Å1 can be partially attributed to the increase in the
average number of hydrogen bonds per water molecule in the
vicinity of the solid-liquid interface. This increased hydrogen bond
number at a strong downward electric field can be explained as fol-
lows. When field strengths are large enough, more hydrogen bonds
in the bulk nanodroplet break owing to the directional arrange-
ment of water molecules. The water molecules losing hydrogen
bonds are more likely move to the solid-liquid interface and form
hydrogen bonds again, leading to the increased hydrogen bond
number in the vicinity of the solid-liquid interface. The averge
number density of water molecules in the z-direction is also
extracted. Here, the nanodroplet is divided into multiple layers
with a 3 Å layer thickness, and the number density in each layer
is calculated. As shown in Fig. 8, the number density near the
solid-liquid interface follows the same trend as that with an
6
increases with increasing the downward field strength. As shown
in Fig. 4, when the downward field strength is larger than
0.05 V Å1, the local number density of water molecules in the
vicinity of the triple line starts to decrease. This result indicates a
weaker pinning effect, which enhances infiltration of the sus-
pended liquid into nanogrooves and thus promotes spreading of
the nanodroplet. Accordingly, the weaker pinning also contributes
to the decreased static contact angle at high downward field
strengths.
3.3. Effect of field direction
It is widely recognized that electrowetting of macrodroplets
does not depend on the field direction. However, a recent study
has shown that with the same field strength, static contact angles
of a nanodroplet on a smooth surface are not equal when upward
and downward electric fields are applied [23]. In this section, the
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al.
effect of the field direction is further examined on a nanostruc-
tured surface. Fig. 9 shows the snapshots of nanodroplet spreading
in the presence of an upward electric field. The comparison among
Figs. 2, 6 and 9 indicates that there is no significant difference
between upward and downward electric fields at low field
strengths. Five nanogrooves are infiltrated by the equilibrated nan-
odroplet at E = 0.03 and 0.05 V Å1 regardless of the field direction.
However, the difference starts to emerge at high field strengths,
especially at E = 0.09 V Å1 six nanogrooves are infiltrated under
the downward electric field, whereas only four nanogrooves are
infiltrated under the upward electric field. Another significant dif-
ference at E = 0.09 V Å1 lies in that the equilibrated nanodroplet is
a hemisphere under the downward electric field, whereas it is
elongated vertically, forming a hemi-ellipsoid under the upward
electric field.
As shown in Fig. 7, unlike under the downward electric field, the
static contact angle always increases with the field strength under
the upward electric field. Almost the same static contact angles are
observed under both electric fields when E  0.05 V Å1, above
which a larger static contact angle occurs under the upward elec-
tric field. The static contact angle is 76.5° at E = 0.09 V Å1 under
the upward electric field, 41° higher than that under the down-
ward electric field.
The difference at high field strengths between the upward and
downward electric fields can be partially attributed to different
movement trajectory of water molecules. At low field strengths,
only a small number of hydrogen bonds break in the bulk liquid,
and hence, the number of water molecules that migrate from the
(a)
0 ps 38 ps 72 ps
(b)
0 ps 30 ps 44 ps
(c)
0 ps 34 ps 154 ps
(d)
0 ps 30 ps 70 ps
Fig. 9. Morphology evolution of a water nanodroplet on a nanostructured surface in the presence of an upward electric field at: (a) E = 0.03 V Å1; (b) E = 0.05 V Å1; (c)
E = 0.07 V Å1; and (d) E = 0.09 V Å1.
Journal of Molecular Liquids 333 (2021) 116039
bulk liquid to the liquid-gas or solid-liquid interfaces is hardly
affected by the electric field. The reduction in the number of hydro-
gen bonds in the vicinity of the solid-liquid interface arises only
from applying the electric field. Therefore, the average number of
hydrogen bonds in this region are almost the same under the
upward and downward electric fields when the field strength
remains constant, as shown in Fig. 3. At high field strengths, more
hydrogen bonds break in the bulk liquid, increasing the chance of
migration of water molecules to the interfaces. The difference
between the upward and downward electric fields lies that water
molecules in the bulk liquid more likely migrate to the solid-
liquid interface and forms hydrogen bonds again under the down-
ward field, but to the liquid-gas interface under the upward field.
As the result of different movement trajectory of water molecules,
the average number of hydrogen bonds increases at high field
strengths under the downward electric field but decreases under
the upward electric field, as shown in Fig. 3. Thus, the solid-
liquid interfacial tension always increases with the field strength
under the upward electric field, leading to the continuously
increased static contact angles. Moreover, the local number den-
sity, as shown in Fig. 4, indicates that the pinning effect is always
enhanced under the upward field, and the pinning force monoto-
nously increases with the field strengths, which is another reason
for the continuously increased static contact angles under the
upward electric field.
Fig. 10 shows the evolution of spreading radius for the water
nanodroplet with or without an upward electric field. The spread-
ing rate in the early spreading stage are almost the same at various
360 ps 478 ps 558 ps 2000 ps
72 ps 338 ps 1028 ps 2000 ps
352 ps 542 ps 1358 ps 2000 ps
318 ps 966 ps 1448 ps 2000 ps
7
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al. Journal of Molecular Liquids 333 (2021) 116039

100 of h0 = 50°, 42°, and 32° in the presence of a downward electric

90 field with E = 0.05 V Å1.
80
70 Fig. 11 shows the snapshots of nanodroplet spreading for the
60 three intrinsic contact angles. As the surface becomes more wet-
50 table, more nanogrooves are infiltrated by the nanodroplet. Only
40 five nanogrooves are infiltrated at h0 = 60°, whereas the number
R (Å)

increases to 7, 8, and 9 at h0 = 50°, 42°, and 32°, respectively. As

30 mentioned before, the reorientation of polar water molecules trig-
E= 0 V Å-1 gered by electric fields may make hydrogen bonds break. However,
20 E= -0.03 V Å-1 the enhanced intrinsic wettability means stronger interactions
E= -0.05 V Å-1 between gold atoms and water molecules, which hinders the reori-
E= -0.07 V Å-1 entation of water molecules in the vicinity of the solid-liquid inter-
E= -0.09 V Å-1 face, thereby preventing hydrogen bonds from breaking. As shown
10 in Fig. 12, the average number of hydrogen bonds in the vicinity of
0.1 1 4 the solid-liquid interface increases when the surface becomes
t (ns) more wettable, leading to a reduced solid-liquid interfacial tension
and hence an enhanced capillary force, which promoting spreading
Fig. 10. Evolution of spreading radius of a water nanodroplet on a nanostructured
surface in the presence of an upward electric field.

3.23

field strength and is equal to that under the downward electric 3.22
field, indicating that the spreading kinetics is not affected by the
field direction. In the later spreading stage, different spreading 3.21
kinetics is observed between both fields. The spreading rates under
3.20
<nHB>
the upward electric field are always lower than those under the
downward electric field. This result again confirms that spreading
3.19
of the nanodroplet is suppressed by the upward electric field and
the suppression becomes more significant at high field strengths. 3.18
E= 0 V Å
-1

3.17
E= -0.05 V Å
-1

3.4. Effect of intrinsic wettability

3.16
It is worth noting that the intrinsic wettability may influence 30 32 34 36 38 40 42 44 46 48 50 52
the formation of hydrogen bonds as well as the pinning, electro-
wettability, and electro-stretching effects, especially for a nan-
odroplet spreading on a nanostructured surface. In this section, Fig. 12. Average number of hydrogen bonds per water molecule in the vicinity of
simulations are implemented on the nanostructured surface with the solid-liquid interface on a nanostructured surface with various intrinsic
the same aspect ratio of h/w = 1 but different intrinsic wettability wettability in the presence of a downward electric field at E = 0.05 V Å1.

(a)

0 ps 22 ps 166 ps 542 ps 770 ps 1106 ps 2000 ps

(b)

0 ps 24 ps 116 ps 298 ps 938 ps 1308 ps 2000 ps

(c)

0 ps 28 ps 46 ps 316 ps 894 ps 1356 ps 2000 ps

Fig. 11. Morphology evolution of a water nanodroplet on a nanostructured surface with various intrinsic wettability in the presence of a downward electric field at
E = 0.05 V Å1: (a) h0 = 50°; (b) h0 = 42°; and (c) h0 = 32°.

8
Ben-Xi Zhang, Shuo-Lin Wang, X. He et al.
θ0=32
100 θ0=42
θ0=50
R (Å)
10
0.01 0.1 1 4
t (ns)
Fig. 13. Evolution of spreading radius of a water nanodroplet on a nanostructured
surface with various intrinsic wettability in the presence of a downward electric
field at E = 0.05 V Å1.
of the nanodroplet on the nanostructured surface. On the basis of
an analysis of the local number density, it is found that the
enhanced intrinsic wettability also decreases the pining force in
the triple line region. Moreover, our previous study has demon-
strated that the enhanced intrinsic wettability reduces the energy
barrier for the wetting transition from the Cassie state to Wenzel
state [41]. Therefore, the reduced pinning and energy barrier for
the wetting transition are responsible for the fact that more nano-
grooves are infiltrated by the nanodroplet. Fig. 13 shows the evolu-
tion of spreading radius for the three intrinsic contact angles. In the
late spreading stage, the enhanced intrinsic wettability promotes
the nanodroplet spreading. Likewise, this result can be explained
by the reduced static contact angle.
4. Conclusions
In this study, the spreading of a water nanodroplet over a
nanostructured surface in the presence of a vertical electric field
are investigated via MD simulations. The field strength, field direc-
tion, and intrinsic wettability of the surface are altered to under-
stand the statics and dynamics of wetting of the nanodroplet.
The main conclusions are as follows.
(1) In the presence of an electric field, electric field forces make
polar water molecules reorient themselves, forming a direc-
tional arrangement along the field direction. The directional
arrangement induces an electro-stretching effect and hence
hinders the spreading. The directional arrangement also
leads to the breaking of hydrogen bonds both in the bulk liq-
uid and in the vicinity of the solid-liquid interface. Owing to
the breaking of hydrogen bonds in the bulk liquid, water
molecules are more likely to migrate to the solid-liquid or
liquid-gas interface, accelerating the spreading, referred to
as an electro-wettability effect. The breaking of hydrogen
bonds in the vicinity of the solid-liquid interface increases
the solid-liquid interfacial tension, thereby decreases capil-
lary force and hindering the spreading. Moreover, the elec-
tric field also alters the pinning force in the vicinity of the
triple line. Thus, the electro-stretching, electro-wettability,
modified solid-liquid interfacial tension, and pinning jointly
affect the statics and dynamics of wetting of nanodroplets
on nanostructured surfaces.
(2) When a downward electric field is applied to the nan-
odroplet, the spreading is first hindered and then is pro-
moted with increasing the field strength, leading to a first
increased and then decreased static contact angle. However,
9
Journal of Molecular Liquids 333 (2021) 116039
when applying an upward electric field, the spreading is
always hindered, and the static contact angle monotonously
increases with the field strength. The increased solid-liquid
interfacial tension and the enhanced pinning effect are
found to be responsible for the increased static contact angle
for both electric fields at low field strengths. The difference
at high field strengths between both electric fields is par-
tially attributed to different movement trajectory of water
molecules in the bulk liquid. As a result, the average number
of hydrogen bonds increases at high field strengths under
the downward electric field but decreases under the upward
electric field. Moreover, the pinning effect is always
enhanced under the upward field, whereas it is weakened
at high field strengths under the downward field, which is
another reason for different statics and dynamics of wetting
at high field strengths between upward and downward elec-
tric fields.
(3) A small intrinsic contact angle means strong interactions
between the nanodroplet and surface, which suppresses
the breaking of hydrogen bonds in the presence of an electric
field, thereby reducing the solid-liquid interfacial tension
and promoting the spreading. The small intrinsic contact
angle also reduces the pinning force at the triple line as well
as the energy barrier of the Cassie-Wenzel wetting transi-
tion, and hence, more nanogrooves are infiltrated by the
nanodroplet, leading a reduced static contact angle.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This study was partially supported by the State Key Program of
National Natural Science of China (No. 51936004), Science Fund for
Creative Research Groups of the National Natural Science Founda-
tion of China (No. 51821004), and the Fundamental Research
Funds for the Central Universities (No. 2020MS063).
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