International Journal of Heat and Mass Transfer 79 (2014) 846–857

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International Journal of Heat and Mass Transfer

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

Structure and transport properties of liquid alkanes in the vicinity

of a-quartz surfaces
Hari Krishna Chilukoti a,⇑, Gota Kikugawa b, Taku Ohara b
a
Department of Nanomechanics, Graduate School of Engineering, Tohoku University, Sendai, Japan
b
Institute of Fluid Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan

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

Article history: Structure and mass transport properties of several liquid n-alkanes, methane, decane and tetracosane, in
Received 8 November 2013 the vicinity of a-quartz surfaces of three crystal planes have been investigated by using molecular
Received in revised form 27 May 2014 dynamics simulations. Solid a-quartz surfaces were terminated with –H and –OH groups to create hydro-
Accepted 31 August 2014
phobic and hydrophilic surfaces, respectively. It was observed that adsorption of the liquid alkane mol-
Available online 19 September 2014
ecules is more noticeable near the (0 0 1) crystal plane when compared with other two planes (0 1 1) and
(1 0 0). For a given alkane, the number of molecules adsorbed near a a-quartz wall marginally depends
Keywords:
upon the crystal plane and type of surface termination. Ordering parameter and radius of gyration for
Molecular dynamics
Solid–liquid interface
liquid molecules were examined in the interface region to gain the knowledge about molecular alignment
n-Alkane and chain configuration in the interface region. Liquid molecules in the first adsorption layer near the
a-Quartz hydrophilic and hydrophobic surfaces are more parallel to the interface in the following order (0 0 1),
Crystal plane (0 1 1) and (1 0 0). Portions of decane and tetracosane liquid molecules tend to enter into the H-termi-
Self-diffusion coefficient nated side with an orientation in the parallel direction to the interface and into the OH-terminated side
with an orientation in the perpendicular direction for (1 0 0) crystal plane. Molecules are flattened in the
direction perpendicular to the interface and are elongated in the other direction in the interface region for
decane and tetracosane. It is observed that the in-plane self-diffusion coefficient of liquids, the self-dif-
fusion coefficient according to the migration of molecules in the directions parallel to the interface, is
smaller in the vicinity of the solid surface and approaches to the bulk liquid value away from the inter-
face. For methane, decane and tetracosane, the in-plane diffusion in the first adsorption layer near the
smoother silica surface (0 0 1), which has molecularly smoother surface than the other two surfaces
(0 1 1) and (1 0 0), for both of the terminations is higher as compared with the other two surfaces
(0 1 1) and (1 0 0). It was found that the diffusion coefficients in the two directions of the 2-D in-plane
diffusion are different significantly and this anisotropic nature is resulted by the topology of the solid sur-
face. At the same reduced temperature, a tendency was observed that the in-plane diffusion near the
H-terminated and OH-terminated surfaces for three crystal planes increases with an increase in the chain
length of the liquid alkanes.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction structural adhesives used in the aerospace and automotive appli-

The interface between liquid and solid is important in many
industrial applications like catalysis, adhesion, wetting, corrosion
and biocompatibility. Structure and dynamic properties at the
interfaces need to be carefully understood at the molecular level
to design many industrial processes and the proper function of
many devices where interface has significant importance like
⇑ Corresponding author at: Molecular Heat Transfer Laboratory, Institute of Fluid
Science, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577, Japan. Tel./
fax: +81 22 217 5872.
E-mail address: chilukoti@microheat.ifs.tohoku.ac.jp (H.K. Chilukoti).
cation, paints and coatings and microelectronics [1]. It is observed
that liquids behave differently in the vicinity of solid surfaces
from that in the bulk liquid. The chemical and physical nature
of the surface, hydrogen bond network on the surface, atomic-
scale roughness, partial charges on the surface, its distribution
and concentration might influence the transport properties and
structure of liquid in the vicinity of the solid surface [2,3]. From
a scientific point of view, it would be interesting to know how
the interactions between two contacting phases influence the
interfacial physical properties in the macroscopic scale. It is also
important to know how far the influence caused by the solid wall
penetrates into the bulk liquid.

http://dx.doi.org/10.1016/j.ijheatmasstransfer.2014.08.089
0017-9310/Ó 2014 Elsevier Ltd. All rights reserved.
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857
Nomenclature
D self-diffusion coefficient (m2/s)
L length of the simulation system (Å)
N number of molecules
P orientation order parameter
r distance between two united atoms (Å)
rc cut-off radius (Å)
Rg radius of gyration (Å2)
S survival probability
Tcr critical temperature (K)
Due to the hidden nature and comparatively small size (few
molecular lengths), investigations of molecules in the interface
regions by experiments is not straightforward [4]. For instance, it
is difficult to study the liquid confined between solid walls which
are closer than 1 nm from experiments because of large surface
forces [5]. It is also observed that some experimental techniques
like the surface force apparatus (SFA) measurements cannot be
used for investigation of an isolated liquid–solid surface [5]. Sum
frequency generation (SFG) vibrational spectroscopy is a widely
used analytical tool to examine the structure at liquid–solid inter-
faces. Nevertheless, quantitative analysis of the obtained spectra is
not easy. So, computer simulations have been also performed to
obtain the equilibrium and non-equilibrium quantities in the inter-
face region and to understand the experimental findings. Solid/
liquid interfaces are extensively studied by the computational
methods like molecular dynamics simulations. Using this method,
transport, physical and structural quantities are calculated and
analyzed.
Silica is ubiquitously found in the earth crust in the form of
a-quartz. Due to its importance in geology, nanotribology, micro-
fluidics, micro/nanofabrication and to many processes in the nat-
ure, scientists have extensively studied about liquid interaction
with silica surfaces. Liquid alkanes have many industrial applica-
tions like lubrication and coating. It is also important because it
is a basic block of various organic chemicals. Interfaces involving
alkane and silica substrate have been attracting scientific and
engineering interest. For example, studies of structural and trans-
port phenomena of alkanes in the vicinity of silica surfaces have
applications in the oil production industry and MEMS.
The a-quartz/water interface have been extensively studied by
many researchers [2,3,6–8] using MD simulations to understand
the hydrophobic and hydrophilic effect and to examine the struc-
ture of water in the interface. It is well understood that inorganic
oxides like a-quartz has affinity to hydroxyl groups on its surface
[4]. It is believed that fully hydroxylated quartz surfaces are ener-
getically favored and stable when compared with bare and par-
tially hydroxylated surfaces [9]. Wright et al. [10] suggested that
a charge free hydroxylated surface would be a reasonable approx-
imation to a-quartz at the surface at pH7. Therefore, in the present
work one wall is terminated with OH-group (hydroxylated) and
the other wall terminated with H-group (hydrogenated). Both sur-
faces are modeled as electrically neural surfaces.
Mass transport phenomena and the measurement of diffusion
coefficient are important as a fundamental research and also in
applications in industry such as coating, surface processing and
modification by using chemical solutions, and adsorption filtration
of chemical species. Study of diffusion in liquid alkanes under con-
finement at nanoscale has application in molecular sieving in
nanofilters and pore filling in solid-state dye-sensitized solar cells
[11]. It is well known that liquid in the vicinity of solid wall has
847
Greek symbols
h angle between the line joining two united atoms and
interface normal
s time interval (s)
Subscripts
PSk particular slab
x, y, z x, y and z directions
layered structures [12–14]. It would be of practical interest to
know the orientation and shape of the molecules in the layers
and their influence on the diffusion coefficient in these layers,
especially in cases of long-chain polymer liquid molecules. Exper-
imental measurement of diffusion coefficient is sometime difficult
under a circumstance like low concentration limit and far from
ambient. Under these conditions computational simulations have
an advantage. MD simulations are widely used to evaluate the dif-
fusion of liquid in the bulk liquid region [15–17] and liquid in the
vicinity of solid substrates [18–20]. Recently, diffusion in the inter-
face region was studied by a few researchers using modified
Einstein relation [21–23]. The authors have examined the diffusion
in several alkane liquids at the liquid–vapor interfaces [24].
The transport properties of liquid alkanes in the vicinity of silica
substrates are not well understood issues. Among the possible
crystallographic surfaces of the a-quartz, only a few are more sta-
ble. For each crystallographic plane, surface characteristics are dif-
ferent and the interaction with liquids in the vicinity is also
different. Detailed understanding of influences of crystal plane on
transport properties of liquids at the interfaces helps to control
the mobility of liquids and diffusion process in the vicinity of solid
surfaces. To the best of our knowledge, self-diffusion of alkanes in
the vicinity of silica substrates has not been investigated by any
researcher.
In the present study, structure and diffusion properties of liquid
methane (CH4), decane (C10H22) and tetracosane (C24H50) in the
vicinity of a-quartz substrates were investigated by molecular
dynamics simulations. To examine the influence of a-quartz sur-
face topology, obtained properties in the interface region were
compared among (0 0 1), (0 1 1) and (1 0 0) crystal planes. The sys-
tems utilized in the present MD simulations have two a-quartz sil-
ica walls contacting the alkane liquid between the walls. One of the
a-quartz substrate surfaces was terminated with –H (silane)
groups and the other wall surface with –OH (silanol) groups to
generate hydrophobic and hydrophilic surfaces, respectively. The
properties of liquid alkanes near –H and –OH terminated surfaces
were compared to examine the effect of surface termination type.
By comparing the properties of liquid alkanes at the same reduced
temperature, influences of alkane chain length have been studied.
2. Potential functions and simulation methodology
MD simulations have been performed in the present study to
investigate the structure and self-diffusion coefficient of different
liquid alkanes in the vicinity of (0 0 1), (1 0 0) and (0 1 1) crystal
planes of a-quartz substrate. Methane (CH4), decane (C10H22) and
tetracosane (C24H50) were selected for the n-alkanes. An atomistic
model of silica was applied and alkane liquid was modeled using
the united atom model. In the united atom representation of
alkane, CHn groups are treated as single interaction site and the
848 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857
interaction site is placed at the carbon atoms. In the literature,
many united atom force fields have been developed to reproduce
physical and dynamic properties of alkanes using MD simulations.
Among those, NERD potential parameters were used for decane
and tetracosane in the present study, and TraPPE parameters for
methane. Stretching of C–C bonds, bond bending and torsional
motion are considered as intra molecular degrees of freedom.
Intermolecular interaction between atoms on different molecules
and intramolecular interaction between atoms which are more
than 3 atoms apart within an alkane molecule are considered using
LJ potential. Detailed force field parameters for alkanes were found
in [25,26]. The silica wall was modeled based on the all atom
model. Lopes et al. [27] proposed a force field for silica by optimiz-
ing the CHARMM force field from ab initio calculations. Among the
available force fields in the literature, this force field is in compat-
ible with NERD force filed [25] and TraPPE force field [26]. So, this
was used to model the a-quartz substrate. Interaction parameters
between the atoms in the silica wall were available in Lopes et al.
[27]. In the present simulation, n-alkane molecules and the
a-quartz substrate were interacted through LJ potential. For the
interaction parameter between different species of interaction
sites, the Lorentz–Berthelot rule was used. Coulombic interactions
were calculated using SPME method [28] with a charge grid of
about 1 Å. Cut-off radius (rc) for the LJ interaction was 16 Å.
Atomic equations of motion were integrated with the reversible
reference system propagator algorithm method [29] with multiple
time scales. 1 fs and 0.2 fs integration time steps were used for the
intermolecular and intramolecular motions. Fig. 1 shows the MD
simulation model of the a-quartz solid and alkane liquid system.
The simulation system has two solid silica walls with surfaces par-
allel to the xy plane and an alkane liquid is in between them. In
accordance with the length of the alkane molecule, several sizes
of the systems were created in such a way that the lengths of the
solid substrate in the x, y and z directions were larger than double
of the alkane molecular length. The solid substrate length in the z-
direction was also chosen in such a way that the interaction
between OH-terminated surface and H-terminated surface was
negligible, so that each of the two solid surfaces is not affected
by the other surface beyond the periodic boundary. The length of
the simulation system in the z-direction was 150 Å in all the cases
considered in the present study. Periodic boundary conditions
were applied in all three directions. The a-quartz substrate was
created in such a way that the crystal plane required to contact
the liquid is normal to the z-axis. The solid wall was constructed
by considering the crystal parameters of silica as specified by Lopes
et al. [27]. As suggested by Lopes et al. [27], all the dangling bonds
presented on one of the two surfaces were manually saturated by
terminating with –H atoms to generate a hydrophobic surface and
the other surface was terminated with –OH atoms to generate a
hydrophilic surface, although this kind of silica substrate is an
Fig. 1. The a-quartz (0 0 1) /methane simulation system.
idealized crystal structure and real structure of silica surface is
not completely known [30].
Initially, density of the liquid alkane at a required temperature
was calculated from liquid–vapor interface simulation. After that,
alkane molecules were randomly placed between the two solid
walls to see to it that after the system reaches equilibrium, liquid
density in the bulk liquid region that is sufficiently distant from
the solid walls and free from the influence of intermolecular poten-
tial of the solid wall atoms was close to that of the bulk liquid
alkane obtained at the required temperature. After that, the system
temperature was slowly raised to the required temperature, where
the temperature was controlled using the velocity scaling method.
After the system reached the required temperature, the simulation
system was equilibrated for 5 ns and then a production run was
performed for 3 ns in the NVT ensemble using Nosé–Hoover ther-
mostat for analysis.
3. Results and discussion
3.1. Density profiles
Structure and mass transport properties were obtained after the
system reached equilibrium. First, mass density distributions of
liquid alkane between the two solid walls were examined before
studying other quantities at the interfaces. These density profiles
will provide a basic insight into the structure in the interface
region. In the present study, the results for methane, decane and
tetracosane were compared at the same reduced temperature
(0.56Tcr). Predictions of the critical temperatures for decane and
tetracosane modeled by NERD force field and methane by TraPPE
force field are taken from the literature [26,31] as 191 K, 617 K
and 805 K, respectively, which are used to determine the reduced
temperatures. Bulk liquid densities of the alkanes by the present
simulations have been validated with literature [24]. The density
distributions were obtained by dividing the rectangular simulation
box into slabs with a thickness of 0.1 Å in the z direction, and mea-
suring the density in each slab. Density profiles for liquid methane,
decane and tetracosane at 106.96 K, 345.6 K and 450 K near the
hydroxylated and hydrogenated surfaces are shown in Figs. 2–4.
The origin for the distance in the density profiles is located at the
equilibrium position of the first layer of silicon atoms on which
the surface terminations are attached. Since for the (0 1 1) crystal
plane, the surface atoms are not in a single plane, the origin repre-
sents average position of all the surface silicon atoms. As expected,
density profiles for all alkane liquids exhibit oscillatory nature in
the vicinity of the solid walls. The oscillations in the density profile
indicate layering of liquid molecules in the interface region. The
adsorption layer is defined here as the first layer of liquid mole-
cules near the solid wall which can be identified as the first peak
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857 849

(a) 2500 (a) 2500

Methane at 106.96 K Decane at 345.6 K
2000 2000
H-terminated side H-terminated side
Density (kg/m3)

Density (kg/m3)
1500 (001)
1500
(001) (011)
(011) (100)
1000 (100) 1000

500 500

0 0
-40 -30 -20 -10 0 -40 -30 -20 -10 0
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)

(b) 2500 (b) 2500

Methane at 106.96 K Decane at 345.6 K
2000 2000 OH-terminated side
OH-terminated side
Density (kg/m3)

Density (kg/m3)
1500 1500 (001)
(001) (011)
(011) (100)
1000 (100) 1000

500 500

0 0
0 10 20 30 40 0 10 20 30 40
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)

Fig. 2. Density distributions for methane at 106.96 K on (a) the H-terminated side Fig. 3. Density distributions for decane at 345.6 K on (a) the H-terminated side and
and (b) the OH-terminated side. (b) the OH-terminated side.

in the density profile. For all density profiles, oscillations disappear
after some distance away from the wall and show a flat region
which indicates the bulk-like liquid region which is free from the
influence of solid surfaces. It is observed from the figure that the
layered structure near the (1 0 0) crystal plane is relatively close
to the surface layer of silicon atoms than those for the other two
crystal planes. It suggests that some liquid molecules might enter
into the cavities on the solid surface, which will be examined later
again. Snapshots of the methane/a-quartz interface for all cases of
crystal planes for H- and OH-terminations are shown in Fig. 5. It is
observed in the figure that surface topology is different among the
tested crystal planes, and that shape and orientation of the surface
termination group, –H or –OH, are different for each crystal plane.
The (0 0 1), (1 0 0) and (0 1 1) crystal planes have surface terminal
densities of 10.02OH (or) H/nm2, 7.68OH (or) H/nm2, 5.92OH (or)
H/nm2, respectively. It can be seen in Fig. 5(a) and (c) that methane
molecules in the adsorption layers on the (0 0 1) H- and OH-termi-
nated surfaces and (1 0 0) H-terminated surface are aligned in a
plane. Therefore, it exhibits a simple peak in the density profile
in Fig. 2(a) and (b). In cases of (0 1 1) H- and OH-terminated sur-
faces and (1 0 0) OH-terminated surface, which have larger lat-
tice-scale roughness than (0 0 1), methane molecules in the first
adsorption layer are not aligned in a single plane in a simple fash-
ion. They tend to be located at two typical positions of z. This
results in the split twin peaks in the density profiles in Fig. 2. In
such cases, the first adsorption layer is defined as the twin peaks
instead of the single peak only. When large number of molecules
accumulated, split twin peak is transformed into two simple peaks
(two layers of molecules) which can be observed in Fig. 2(a) for
(1 0 0) crystal plane. In this case, it is observed that the peak density
in the second layer is larger than that in the first layer. For longer
chain molecules, decane and tetracosane, the alignment of liquid
molecules in the adsorption layer is not sensitive to the surface
roughness so that the twin peaks of the adsorption layer disap-
pears. Fig. 2 illustrates that the number of oscillations formed near
the hydrophilic and hydrophobic surfaces and their propagation
into the bulk liquid region is strongly depends on the crystal plane
and the surface termination type for methane. On the other hand,
for decane and tetracosane, layering caused by the wall disappears
approximately at the same distance away from the wall irrespec-
tive of the surface termination type and crystal plane. The layered
structure of liquid molecules is reduced with an increase in chain
length for all crystal planes at the same reduced temperature. Den-
sity of all three liquids in the adsorption layer near hydrophilic and
hydrophobic surfaces for (0 0 1) crystal plane is higher than that of
(0 1 1) and (1 0 0) planes. This can be attributed to the strong inter-
action between (0 0 1) crystal plane and the liquid molecules,
which has a higher surface density of terminal groups than other
two planes. The maximum density in the adsorption layer is higher
on the H-terminated side for methane for all crystal planes,
whereas the maximum density for decane and tetracosane in the
adsorption layer depends on the type of crystal plane.
850 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857

(a) 2500 (a)

Tetracosane at 450 K
2000 H-terminated side
Density (kg/m3)

(001)
1500
(011)
(100)

1000

500

0 (001) OH-side (001) H-side

-40 -30 -20 -10 0
Distance from surface Si atoms (Å) (b)

(b) 2500
Tetracosane at 450 K
2000 OH-terminaetd side
Density (kg/m3)

1500 (001)
(011)
(100)
1000

500 (011) OH-side (011) H-side

(c)
0
0 10 20 30 40
Distance from surface Si atoms (Å)

Fig. 4. Density distributions for tetracosane at 450 K on (a) the H-terminated side
and (b) the OH-terminated side.

Table 1 shows the penetration depths of the liquid methane,

decane and tetracosane into the solid wall for three crystal
planes. The penetration depth is defined here as the overlapping
length of the number density profiles of the liquid atoms and
the solid atoms as shown in Fig. 6. Zoomed region of the number
density profiles of the methane and the silica near the OH-termi-
nated side is shown in the Fig. 6. It is to note that, the chances of (100) OH-side (100) H-side
liquid molecules entering into the cavities on the solid surface are
very rare, which can be seen in the Fig. 5(a) and (b). However, the Fig. 5. Snapshots of OH-terminated (left) and H-terminated (right) a-quartz/
time-averaged number density profiles of liquids atoms and solid methane interfaces for crystal plane of (a) (0 0 1), (b) (0 1 1), and (c) (1 0 0).
atoms are overlapping as shown in Fig. 6. The penetration depth
suggests the tendency of the liquid molecules to enter into the molecules. This tendency might have been influenced by large
cavities on the solid wall. From Table 1, it is observed that at lattice vibrations of termination groups at high temperature. It
the same reduced temperature, liquid tetracosane molecules should be noted that the liquids were simulated at the same
show the tendency to enter deeply into the solid wall near both reduced temperature, which resulted in higher absolute tempera-
types of surface terminations than methane and decane liquid tures for longer alkane molecules. For all liquids, the tendency of

Table 1
Comparison of penetration depth of liquid molecules into the solid wall among methane, decane and tetracosane for three crystal planes.

(0 0 1) Crystal plane (0 1 1) Crystal plane (1 0 0) Crystal plane

H-terminated sideÅ OH-terminated side Å H-terminated side Å OH-terminated side Å H-terminated side Å OH-terminated side Å
Methane (CH4) – – 0.1 0.7 0.4 0.7
Decane (C10H22) – 0.1 0.5 1.0 0.9 2.1
Tetracosane (C24H50) 0.2 0.6 0.7 1.3 1.2 2.2
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857 851

×1028 ×1028
15.0 (a) 0.5 10.0
Number density Decane at 345.6 K

Orientation order parameter

12.5 of silica atoms
H-terminated side 8.0
Methane at 106.96 K

Number density (m-3)

0.25
Number density (m-3)

(001)
10.0 (011) crystal plane
(011) 6.0
Number density (100)
7.5 of methane atoms
0 4.0
Penetration
5.0 depth
2.0
2.5 -0.25 Number density
of H-termination
0.0
0.0
-0.5 -2.0
-2.5 -40 -30 -20 -10 0
2 2.5 3 3.5 4 Distance from surface Si atoms (Å)
Distance from surface Si atoms (Å)
28
Fig. 6. Number density profiles of silica atoms and methane atoms for (0 1 1) crystal ×10
plane near OH-termination side. (b) 0.5 10.0
Decane at 345.6 K

Orientation order parameter

molecules penetration is deeper into the OH-terminated surface OH-terminated side 8.0

Number density (m-3)

than the H-terminated surface. 0.25
(001)
Table 2 shows the widths of the first adsorption layer in cases 6.0
(011)
of methane, decane and tetracosane in the vicinity of –H and –OH (100)
terminated three a-quartz crystal planes where the width of the
0 4.0
first adsorption layer is defined as the distance from the valley
between 1st and 2nd adsorption layer to the point where the
traces of liquid molecules are present close to the solid wall for 2.0
both type of terminations. The value in the bracket in the table -0.25 Number density
indicates average number of molecules contained in the first of OH-termination
0.0
adsorption layer per cross sectional area of the interface. Average
number of molecules was calculated by dividing the total number
-0.5 -2.0
of united atoms in the first adsorption layer with the number of 0 10 20 30 40
united atoms in a molecule. It is observed that the adsorption Distance from surface Si atoms (Å)
width near OH-terminated surface is larger than near H-termi-
nated surface for (0 1 1) and (1 0 0) crystal planes. On the other Fig. 7. Orientation order parameter distributions for decane at 345.6 K on (a) the H-
terminated side, and (b) the OH-terminated side. Density distribution is also plotted
hand, for (0 0 1) crystal plane the adsorption width on H-termi-
in the figure by the dashed lines and dash dotted lines.
nated surface is larger than the OH-terminated surface. It is
observed that the average number of molecules present in the
first adsorption layer per cross-sectional area of the interface on plane on the ordering of molecules in the layers of liquid molecules
the –H terminated side is slightly larger than the –OH terminated close to the solid wall. This represents the average alignment of
side for all three crystal planes. For a particular alkane, the num- molecules in the liquid and interface region. The orientation order
ber of molecules in the first adsorbed layer per cross sectional parameter is defined as follows [32]
area of the interface on both sides of terminations slightly
depends upon the crystal plane. 1 
PðzÞ ¼ 3 cos2 h  1 ; ð1Þ
2

3.2. Orientation order parameter and radius of gyration where h is defined as the angle between connecting line between
two united atoms which are separated by two covalent bonds in
The orientation order parameter was examined in order to an alkane molecule and a normal vector to the interface plane (z-
know how the molecules are aligned and the influence of crystal direction). The angular bracket represents that averages are taken

Table 2
Comparison of the first adsorption layer width for methane, decane and tetracosane for three crystal planes. Numbers in the bracket indicate the average number of molecules in
the first adsorption layer per cross sectional area of the interface.

(0 0 1) Crystal plane (0 1 1) Crystal plane (1 0 0) Crystal plane

H-terminated side Å OH-terminated side Å H-terminated side Å OH-terminated side Å H-terminated side Å OH-terminated side Å
(Å2) (Å2) (Å2) (Å2) (Å2) (Å2)
Methane (CH4) 3.00 (0.06131) 2.60 (0.06029) 2.30 (0.05924) 2.70 (0.05923) 4.00 (0.07684) 4.15 (0.06720)
Decane (C10H22) 4.40 (0.01434) 4.25 (0.01426) 4.00 (0.01455) 4.20 (0.01393) 5.00 (0.01457) 5.90 (0.01375)
Tetracosane 4.75 (0.00631) 4.70 (0.00624) 4.30 (0.00652) 4.40 (0.00595) 5.40 (0.00639) 6.20 (0.00619)
(C24H50)
852 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857

28 −19
×10 ×10
(a) 0.5 10.0 (a) 7.0 2500
Tetracosane at 450 K Tetracosane at 450 K
Orientation order parameter

H-terminated side 8.0 H-terminated side

6.0 2000

Number density (m-3)

0.25
(001) (001)

Density (kg/m3)
(011) 6.0

Total R2g (m2)

(011)
(100) 5.0 (100) 1500
0 4.0

4.0
Radius of gyration 1000
2.0
-0.25 Number density
of H-termination Density
0.0 3.0 500

-0.5 -2.0 2.0 0

-40 -30 -20 -10 0 -40 -30 -20 -10 0
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)

×10
28 ×10−19

(b) 0.5 10.0 (b) 7.0 2500

Tetracosane at 450 K Tetracosane at 450 K
Orientation order parameter

OH-terminated side 8.0 OH-terminated side

6.0 2000
Number density (m-3)

0.25

Density (kg/m3)
(001) (001)
6.0
Total Rg2 (m2)
(011) (011)
5.0 1500
(100) (100)
0 4.0
4.0 Radius of gyration 1000
2.0
-0.25 Number density Density
of OH-termination 3.0 500
0.0

-0.5 -2.0 2.0 0

0 10 20 30 40 0 10 20 30 40
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)

Fig. 8. Orientation order parameter distributions for tetracosane at 345.6 K on (a) Fig. 9. Total radius of gyration as a function of distance for tetracosane at T = 450 K
the H-terminated side and (b) the OH-terminated side. Density distribution is also on (a) the H-terminated side and (b) the OH-terminated side. Density distribution is
plotted in the figure by the dashed lines and dash dotted lines. also plotted in the figure.

over all the vectors present in a particular slab over the entire
production run. It has maximum value of 1 and minimum of
0.5. Zero value of the ordering parameter indicates that alkyl chain
segments are oriented randomly. A positive value specifies that
molecular orientation is favored parallel to the z-direction, i.e., per-
pendicular to the interface. A negative value indicates that favored
orientation is perpendicular to the z-axis and parallel to the inter-
face. Variation of the ordering parameter along the z-axis was
obtained by dividing the rectangular simulation box into slabs with
a thickness of 1 Å. A vector joining two united atoms was assigned
to a slab where the midpoint was situated.
Variation of the orientation order parameter along the z-direc-
tion for decane and tetracosane at the same reduced temperature
were shown in Figs. 7 and 8. Density profiles of alkane liquids mol-
ecules were shown in the figures as dashed lines. Density profiles
of –H and –OH surface termination groups for (1 0 0) crystal plane
are also shown in the figure by the dash dotted line. As expected,
molecules are randomly oriented in the bulk liquid region. Accord-
ing to the oscillations in the density profile, the orientation order
parameter exhibits oscillations between positive and negative val-
ues. The value is negative in the layers of molecules located at the
peaks of the density, while it is weakly positive between the layers.
This indicates that portions of molecules in a layer are bent in the
perpendicular directions to the interface between the two layers
and align preferentially parallel to the interface in the next layer.
This is an indication of interlocking of molecules in the monolayers
which is called as interlayer interdigitation [1]. The amplitude of
oscillation of the orientation order parameter is the largest for
the (0 0 1) surface and smallest for the (0 1 1) surface, although it
is a slight difference. The difference between H-side and OH-side
is also very small.
A remarkable feature is observed in the inner side of the first
adsorption layer for the OH-terminated side of (1 0 0) surface. The
orientation order parameter exhibits large positive value. This
occurs in the region close to the solid surface where the number
density profiles of the liquid molecules and the OH-termination
groups overlap. This implies that a few portions of liquid molecules
tend to get into the solid surface structure with a perpendicular
orientation only in the case of (1 0 0) surface. On the other hand,
the molecules near the H-terminated side might enter into the
solid wall in the parallel orientation. At the same reduced temper-
ature, decane and tetracosane liquids have approximately the same
distributions of the orientation order parameter near the hydro-
phobic and hydrophilic surfaces for a particular crystal plane. Sim-
ilar tendency of orientation ordering is observed for other kinds of
liquids near a-quartz substrates by experiments [5] and MD simu-
lations [1,4].
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857 853

×10
−19 3.3. Self-diffusion coefficient in the vicinity of interface
6.0 3000
(a) Tetracosane at 450 K Diffusion coefficient is commonly obtained by MD simulations
using the Einstein relation and Green–Kubo relation. Recently,
H-terminated side 2500
Liu et al. [21] modified the Einstein relation to determine the
Component of R2g (m2)

4.0 2 self-diffusion coefficient in the heterogeneous systems which is

Rg in x-direction

Density (kg/m )
2000

3
2 applicable to study the diffusion in the interface regions. The var-
Rg in y-direction
iation of the in-plane self-diffusion coefficient, a self-diffusion
2
Rg in z-direction coefficient related to migration of molecules in the direction paral-
2.0 1500
lel to the interface, in the layers of liquid molecules in the vicinity
of the solid wall were analyzed in the present study using this
1000 method. Although the technical details are addressed in Ref. [22],
0.0 the method is briefly described here. The simulation system was
(001) 500 divided into slabs in the z-direction. The survival probability of
(011) the liquid molecules to be present in a slab is obtained from the
(100) following formula:
-2.0 0
-40 -30 -20 -10 0 Nð0; sÞ
Distance from surface Si atoms (Å) SðsÞ ¼ ; ð2Þ
Nð0Þ

−19
where N(0, s) indicates the number of molecules that are continu-
×10 ously present in the slab (PSk) during the entire time period s. Num-
8.0 3000
(b) Tetracosane at 450 K
ber of molecules in the slab at the beginning is represented by N(0).
Molecule was allocated to a slab where the center of mass of the
OH-terminated side 2500 molecule was situated. Mean square displacement in the x direction
6.0
Component of R2g (m2)

of the molecules that are present in the slab is calculated as follows:

2
R in x-direction D E
Density (kg/m )

g
2000 1 X
3

R2g in y-direction DxðsÞ2 ¼ ðxi ðsÞ  xi ð0ÞÞ2 : ð3Þ

4.0
2
Rg in z-direction
2.0
0.0
-2.0
0 10 20
Distance from surface Si atoms (Å)
Fig. 10. Components of radius of gyration as a function of distance for tetracosane
at T = 450 K on (a) the H-terminated side and (b) the OH-terminated side. Density
distribution is also plotted in the figure.
In order to obtain knowledge about shape of the alkane mole-
cules in the interface region, the radius of gyration was examined.
The detailed calculation procedure applied by the authors has been
described in [32,24]. To obtain the variation of the radius of gyra-
tion, the simulation system was divided into slabs with a width of
1 Å. Radius of gyration value of a molecule was allocated to a slab
where the center of mass of the molecule was situated. The
mean-squared total radius of gyration for tetracosane near the
hydrophobic and hydrophilic surfaces, averaged within the slabs
are shown in Fig. 9 for three crystal planes, and the component of
the radius of gyration decomposed into the x, y and z direction
are shown in Fig. 10. The density distributions are also plotted in
both figures. It is observed from the figures that the total radius
of gyration is constant in the bulk liquid region and increases stee-
ply in the first adsorption layers. This suggests that shape of the
alkane molecules is remarkably changed and stretched in the first
adsorption layer in all cases of the three crystal planes and the
two terminations. It is observed from Fig. 10 that the z-component,
which is normal to the solid surface, decreases while the parallel
components increase in the interface region. Based on the observa-
tions of the orientation order parameter and the radius of gyration,
it is evident that molecules are flatten in the z direction and are
extended in the interface planar direction.
PSk Nð0Þ i2PS
k
1500
Utilizing this mean square displacement, self-diffusion coefficient
in the parallel direction was calculated by the following formula:
1000
hDxðsÞ2 iPSk
Dxx ðPSk Þ ¼ lim : ð4Þ
(001) s!1 2sSðsÞ
500
(011)
Using this modified Einstein relation, we can determine the diffu-
(100)
sion coefficient for each slab in the interface region. To observe
0
30 40 the variation of diffusion in the interface region, small thickness
of slabs is required. However, the reliability of the results deterio-
rates when thin slabs are applied, because of the small number of
molecules in the slab. So, there is a compromise between reliability
of result and finite details of diffusion in the interface region.
In the authors’ previous study [24], the modified Einstein rela-
tion has been used to obtain the variation of self-diffusion in the
direction parallel to the interface in the liquid–vapor interface
region. In the present work, the modified Einstein relation was
used to determine the variation of in-plane self-diffusion coeffi-
cient in the solid–liquid interface region in a similar way to the
previous study for liquid–vapor interfaces. To obtain the variation
as a function of distance from the interface, the simulation box was
divided into slabs and the self-diffusion coefficient in each slab was
obtained from the mean square displacement (MSD) versus time
slope. In the present work, a slab thickness of approximately 8 Å
was applied for the bulk liquid region and smaller values for the
interface regions so that the valley to valley (monolayer) in the
density profile for all major peaks is contained in one slab for all
liquids. Fig. 11(a) shows an example of the slabs considered on
the density profile for the case of (0 0 1) crystal plane with liquid
decane. Fig. 11(b) shows the survival probabilities as a function
of time for each slab. It should be noted that the width of slabs
#1–#4 and #12–#15 is smaller than that of slabs #5–#11 and, sur-
vival probabilities decrease in the slabs #3–#4 and #12–#13. It is
observed from the figure that the survival probabilities are remark-
ably higher for the slabs which are next to the solid wall, #1 and
#15, than the slabs in the bulk liquid region. An example of MSD
versus time plots for decane at 345.6 K was shown in Fig. 11(c).
In the bulk liquid region, all lines are almost overlapping each
854 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857

−9
OH-side H-side ×10
(a) 2250 (a) 5.0 2500

15
12
13
14
5 7 8 9

1
6 10 11

2
3
4

Self-diffusion coefficient (m /s)

Self-diffusion coefficient

2
1800
4.0 2000
Density (kg/m3)

Density (kg/m3)
Methane at 106.96 K
1350 H-terminated side
3.0 1500
(001)
900 (011)
2.0 (100) 1000
Dxx
450 Dyy
1.0 500
Density
0
25 50 75 100 125 0.0 0
-50 -40 -30 -20 -10 0
Position-z (Å) Distance from surface Si atoms (Å)
1
(b) Decane at 345.6 K ×10−9
(001) crystal plane (b) 5.0 2500
0.8

Self-diffusion coefficient (m2/s)

Self-diffusion coefficient
Survival probability

slab # 1
slab # 2 4.0 2000
0.6 slab # 3

Density (kg/m3)
slab # 4
Methane at 106.96 K
3.0 OH-terminated side 1500
0.4 (001)
(011)
slab # 5-11 2.0 1000
slab # 12 (100)
0.2
slab # 13 Dxx
slab # 14 Dyy
slab # 15 1.0 500
0 Density
0 5 10 15 20
Time (ps)
0.0 0
0 10 20 30 40 50
×10−20 Distance from surface Si atoms (Å)
(c) 10.0
Fig. 12. Self-diffusion coefficients Dxx and Dyy as a function of position for methane
MSD parallel to the interface (m2)

at 106.96 K on (a) the H-terminated side and (b) the OH-terminated side. The
in OH-side interface density distributions are shown in dash dotted lines and the self-diffusion
8.0 in bulk liquid coefficient profiles are shown in solid lines with rectangular squares.
in H-side interface

Decane at 345.6 K Figs. 12–14 shows the variation of self-diffusion coefficients Dxx
6.0
and Dyy corresponding to the molecular migration in the parallel
(001) crystal plane direction to the interface, i.e., the in-plane self-diffusion coefficient.
4.0 The results for methane, decane and tetracosane at the same
reduced temperature are plotted as a function of distance from
the solid surface. The origin of the solid surface is again the equi-
2.0 librium position of the surface layer of silicon atoms which are ter-
minated with –H or –OH groups. It is observed from the figure that
self-diffusion coefficient is reduced near the solid walls and
0.0 increases as the position is distant from the wall. It approaches
0 2 4 6 8 10
the self-diffusion coefficient value in the bulk liquid region. Meth-
Time (ps) ane, decane and tetracosane liquids have similar in-plane diffusion
Fig. 11. For decane at 345.6 K near (0 0 1) crystal plane, (a) division of slabs on
characteristics near the –H and –OH terminated surfaces for a
density profile, (b) survival probabilities with respect to time for different slabs, and given crystal plane. For methane near the H-terminated side of
(c) mean square displacement as a function of time for different slabs. the (0 1 1) and (1 0 0) crystal planes, diffusion coefficient in the
few layers from the wall is extremely low (almost zero), which
indicates that molecules are strongly bound to the solid wall. Mol-
other. The red lines correspond to the slabs on the H-terminated ecules near the H-terminated surface for the (0 0 1) plane exhibit a
side while the blue lines correspond to the slabs on the OH-termi- certain value. On the other hand, in the side of the OH-terminated
nated side. The lines for the slabs in the interface regions are dis- surface, diffusion coefficient in the first and second adsorption lay-
tinguished from that of lines for the bulk liquid region, which ers is almost zero only in the case of the (0 1 1) plane, and it has
indicates that self-diffusion in the interface region is different from some significant nonzero values in the adsorption layer in other
that in bulk liquid region. cases of the crystal plane. In contrast with the cases of methane,
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857 855

−9 −9
×10 ×10
(a) 5.5 2500 (a) 3.5 2500
Self-diffusion coefficient Self-diffusion coefficent
Self-diffusion coefficient (m /s)

Self-diffusion coefficient (m /s)

2

2
4.4 2000 2.8 2000
Decane at 345.6 K
Tetracosane at 450 K

Density (kg/m3)

Density (kg/m3)
H-terminated side
3.3 1500 2.1
H-terminated side 1500
(001)
(001)
(011)
(011)
2.2 (100) 1000 1.4 1000
(100)

Density Density
1.1 Dxx 500 0.7 Dxx 500
Dyy Dyy
0 0 0 0
-50 -40 -30 -20 -10 0 -50 -40 -30 -20 -10 0
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)

×10−9 ×10
−9

(b) 5.5 2500 (b) 3.5 2500

Self-diffusion coefficient
Self-diffusion coefficient (m /s)

Self-diffusion coefficient

Self-diffusion coefficient (m /s)

2

2
4.4 2000 2.8 2000
Decane at 345.6 K Tetracosane at 450 K
Density (kg/m3)

Density (kg/m )
OH-terminated side

3
OH-terminated side
3.3 1500 2.1 1500
(001) (001)
(011) (011)
2.2 1000 1.4 (100) 1000
(100)

1.1
Density 500 Density
Dxx 0.7 Dxx 500
Dyy Dyy
0.0 0 0 0
0 10 20 30 40 50 0 20 40
Distance from surface Si atoms (Å) Distance from surface Si atoms (Å)
Fig. 13. Self-diffusion coefficients Dxx and Dyy as a function of position for decane at
Fig. 14. Self-diffusion coefficients Dxx and Dyy as a function of position for
345.6 K on (a) the H-terminated side and (b) the H-terminated side. The density
tetracosane at 450 K on (a) the H-terminated side and (b) the OH-terminated side.
distributions are shown in dash dotted lines and the self-diffusion coefficient
The density distributions are shown in dash dotted lines and the self-diffusion
profiles are shown in solid lines with rectangular squares.
coefficient profiles are shown in solid lines with rectangular squares.

decane and tetracosane liquids show a comparatively large value
in the first adsorption layer near the solid wall for a particular crys-
tal plane. For all three tested liquids, in-plane self-diffusion coeffi-
cient Dxx in the adsorption layer contacting the (0 0 1) plane has
higher values than those of the other crystal plane cases on both
terminations. This indicates that molecules migrate relatively fas-
ter on a smoother surface than that on a rough surface. It is
observed in the figure that the self-diffusion coefficient along the
x direction is not same as the diffusion coefficient along the y direc-
tion for (0 0 1) and (1 0 0) crystal planes. Self-diffusion coefficient
values are not significantly different between the x and y directions
for (0 1 1) crystal plane. Fig. 15 shows the surface terminal silica, H-
and OH-terminated atoms of three crystal planes. This anisotropic
character in the in-plane self-diffusion coefficient is due to the dif-
ference in the topology along the x and y directions for a crystal
plane. Fig. 15(a) and (b) illustrates that the lattice-scale surface
roughness is small in the x-direction than that in the y direction.
Because of anisotropy, self-diffusion coefficient in the x-direction
is significantly higher than that in the y-direction for the (0 0 1)
crystal plane near both terminations, which is more obvious in
case of longer liquid molecules.
For decane and tetracosane, near the OH-terminated side, diffu-
sion coefficient in the first adsorption layer is higher in the follow-
ing order of the crystal plane, (0 0 1), (1 0 0) and (0 1 1). On the
H-terminated side of the (0 1 1) and (1 0 0) crystal planes, the diffu-
sion coefficient in the first adsorption layer is approximately equal
and significantly lower than those for the (0 0 1) crystal plane. It
should be noted that the surface terminal density for (1 0 0) crystal
plane is larger than the (0 1 1) crystal plane. It can be concluded
that configuration of solid molecules at the surface has also a sig-
nificant effect on diffusion of liquid molecules contacting the sur-
face. It is also observed that for a particular liquid alkane,
molecules in contact with (0 0 1) crystal plane on the H-terminated
side migrate faster than the molecules in contact with the OH-
terminated side. For (0 1 1) and (1 0 0) crystal planes, molecules
on the OH-terminated side migrate relatively faster than those
on the H-terminated side. This suggests that surface terminal
group has also an influence on in-plane diffusion of alkane. How-
ever its tendency is different among the three crystal planes.
Although the influence of liquid species on the diffusion in the
interface region is hard to be observed because self-diffusion coef-
ficient in the bulk liquid region is not equal even at the same
856 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857
Fig. 15. Snapshots of H-terminated and OH-terminated surface atoms for crystal plane of (a) (0 0 1), (b) (0 1 1), and (c) (1 0 0).
reduced temperature, the tendency can be observed that diffusion
coefficient value in the adsorption layer contacting the solid wall is
higher with larger chain length of molecules. It is suggested from
the result that the roughness of the solid surface, including the
termination groups, has an influence on the diffusion of liquid mol-
ecules in the first adsorption layer.
4. Conclusions
Structure and self-diffusion coefficient of three liquid alkanes in
the vicinity of three crystal planes of a-quartz silica substrate ter-
minated with –H and –OH groups have been investigated using MD
simulations. Density profiles exhibit oscillations that are a charac-
teristic of liquid interfacial region contacting solids. The layering
structure of liquid molecules is different according to the crystal
plane of solid surface and termination type. This is the most obvi-
ous in the case of methane. For long chain alkanes, influence of
crystal plane and termination type on layering of molecules is less
significant. For all the tested alkanes, the tendency of the liquid
molecules to penetrate into the solid wall is deeper on the OH-ter-
minated side compared with that on the H-terminated side. It was
observed that the number of molecules in the first adsorption layer
is slightly dependent upon the crystal plane and type of surface
termination for a given alkane. The parts of alkane molecules that
enter into cavities on the OH-terminated side of (1 0 0) crystal
plane are in the direction perpendicular to the interface whereas
the parts of the molecules that enter into the cavities on the H-ter-
minated side are in the parallel direction. At the same reduced
temperature, decane and tetracosane liquid molecules have similar
tendencies of alignment in the interface region for a particular
crystal plane with both types of terminations. The variation of
radius of gyration across the interfaces suggests the molecular
shape is remarkably flattened in the z-direction in the layers close
to the wall.
The variation of in-plane self-diffusion coefficient of three liquid
alkanes in the vicinity of a-quartz substrate for different crystal
 H.K. Chilukoti et al. / International Journal of Heat and Mass Transfer 79 (2014) 846–857
planes is studied for the first time using MD simulations. It is
observed that self-diffusion is lower near the wall and reaches to
the bulk liquid value away from the walls. It is shown that mole-
cules in touch with the smoother surface (0 0 1) migrate faster than
the molecules in touch with rough surfaces (0 1 1) and (1 0 0). It was
found that the in-plane diffusion characteristics in the adsorption
layer are anisotropic in nature and this is the most noticeable for
the (0 0 1) crystal plane. At the same reduced temperature, self-dif-
fusion coefficient of the tested alkane liquids in the first adsorption
layer in cases of both types of terminations for all the crystal planes
tends to be higher with an increase in chain length of liquid alkane
molecules. From the results, it can be concluded that the surface
topology and surface termination have significant influences on
the diffusion of alkane liquids in the vicinity of a-quartz substrate.
Conflict of interest
None declared.
Acknowledgments
The work reported in this paper was supported by the Grant-
in-Aid for Scientific Research and the Global COE Program ‘‘World
Center of Education and Research for Trans-Disciplinary Flow
Dynamics’’ by the Japan Society for the Promotion of Science
(JSPS).Numerical simulations were performed on the SGI Altix
UV1000 at the Advanced Fluid Information Research Center,
Institute of Fluid Science, Tohoku University.
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