Investigation of Interfacial Properties at Quartz Alkane Interfaces Using Molecular

International Journal of Advanced Research in Engineering and Technology (IJARET), ISSN
0976 6480(Print), ISSN 0976 6499(Online) Volume 4, Issue 3, April (2013), IAEME
68

INVESTIGATION OF INTERFACIAL PROPERTIES AT
-QUARTZ/ALKANE INTERFACES USING MOLECULAR
DYNAMICS SIMULATIONS

Hari Krishna Chilukoti, GotaKikugawa, TakuOhara

Hari Krishna Chilukoti is with Dept. of Mechanical Engineering, Graduate School of Tohoku
University, Aoba-ku, Sendai 9808577, Japan
GotaKikugawa is with Institute of fluid science, Tohoku University, Katahira, Sendai 9808577, Japan

ABSTRACT

In this paper, molecular dynamics simulations were used to study density, orientation order
parameter of liquid decane and tetracosane in the vicinity of (100) OH- and H- terminated silica
(-quartz) surfaces at various temperatures. Decane and tetracosane molecules were modeled using
NERD united atom force field. Silica wall was modeled using Lopes et al. force field.Typical
Hydrophobic and hydrophilic silica surfaces were generated by terminating the surface with hydrogen
and hydroxyl. Adsorption of alkane molecules on both the solid surfaces was observed to be more
remarkable at lower temperature. Orientation of the molecules was studied by examining the orientation
order parameter. It was found that molecules in the firstadsorption layer close to the hydrophilic surface
are arranged more parallel to the interface than the molecules close to the hydrophobic surface.
At a particular temperature decane and tetracosane molecules have similar kind of
alignmentnearhydrophilic/hydrophobic-quartzsurfaces.

Index Terms: -quartz, alkane, interface, ordering parameter, density.

1. INTRODUCTION

Examination of liquids adjacent to solid surfaces play an important role in lubrication, wetting,
chemical and biological process,heterogeneous catalysis, corrosion, catalysis adhesion, and surface
modification in a variety of industrial processes. Fora wide range of above applications, molecular level
understanding of interfaces is important. Molecules show a unique behavior close to interfaces which is
different from that of bulk region. In the vicinity of solid/liquid interfaces migration of liquid molecules
is lower than in the bulk liquid region and viscosity is higher than the bulk liquid region [1].This is
related to the difference in the interaction between the molecules in the bulk liquid and in the interface
region.

INTERNATIONAL JOURNAL OF ADVANCED RESEARCH IN
ENGINEERING AND TECHNOLOGY (IJARET)
ISSN 0976 - 6480 (Print)
ISSN 0976 - 6499 (Online)
Volume 4, Issue 3, April 2013, pp. 68-76
IAEME: www.iaeme.com/ijaret.asp
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IJARET
I A E M E
69

Silica is an abundantly available compound in the form of -quartz.Because of the
importance in geology, nanotribology, biomineralization, biomimetic filed and molecular
engineering, silica interfaces were extensively studied by many researchers[2-15] at a molecular
level. Liquids of hydrocarbon chain molecules have many industrial applications, andhydrocarbon
chains are major building blocks for long polymers.Interfaces of polymer coating on solid surfaces
have many applications such as structural adhesives used in aerospace, paints, MEMS, polymers
used in microelectronics and laser printers. For the proper function of above devices interfaces
should be carefully designed. Molecular understanding of transport and structurecharacteristics at
solid/liquid interfaces of the microstructures built on a silicon wafer have a significant impact on
the success or failure of various processes such as chemical coating and cleaning.One of the
important things to examine is how the liquid polymer molecules are arranged in the presence of
silica wall.The molecular-scale structure of the system will influence the properties of the
nanoscalesystem. So their knowledge is important to realize optimal thermophysical and
mechanical properties.
Few researchers investigated liquid interfaces with silica surfaces using experiments [3, 11].
But it is still difficult to understand the interfacial structure at the molecular level. Therefore,
computer simulations are also performed to study the molecular-scale structure at solid/liquid
interfaces. Computersimulations also provide better understanding of the experimental
result.Toanalyze the molecular-scale structure and transport phenomena, molecular dynamics
(MD) simulation is the best suitable method.Number of studies have been reported for polymers
with reliable inter- and intramolecular potential models.NERD force field is one of them, which is
used by many researchers to simulate coexistence properties of n-alkanes [16-17] and heat
conduction [18].Recently, quartz- water system was studied by many researchers with different
force field for silica [3, 4, 8]. Skelton et al. [8] reported that ClayFF force field accurately describes
the structure of water at the quartz interface. Wright et al. [11] examined the adsorption strength of
amino-acid analogues on different surfaces of quartz. Lopes et al. [3] optimized the empirical
CHARMM force field parameters for silica from abinitio calculations. In the force field of Lopes et
al. [3]parameters for bulk and surface atoms are given in a different manner. This allows flexible
slab surface simulation. Lopes et al. force filed [3] is compatible with NERD force field to build the
system of -quartz solid and alkane liquid. In the present work,-quartz was modeled using Lopes
et al. force field [3].
The -quartz solid wall has a trigonal crystal structure. Among the all possible
reconstructed silicacrystallographic surfaces, only few are found to be more stable.
Eachcrystallographic faces have different structural features.Depending upon the type of
termination unit,different kind of surfaces was generated.Knowledge of how the liquid molecules
are interacted with the quartz surface atoms will help to understand the structural properties of
liquids near solid wall.It is also important to know how far the fluctuations caused by the solid wall
extends into the bulk liquid from the solid wall, which might be influenced by the topology and
termination of the crystallographic surface.Structural properties of solid substrate, such like atomic
scaleroughness and distribution of partially charged groups on the surface, influence the
hydrophobicity and hydrophobicity nature of the substrate [6]. In the present study we mainly
focused on structure of liquid alkane in the vicinity of OH- and H- terminated (100) -quartz
surface.To investigate the structural characteristics of liquid decane and tetracosane in the vicinity
of (100) -quartz surface, we studied average density and orientation order parameter along the
axis perpendicular to the solid surface z-axis. The simulations were performed for three
temperatures and its influences were examined.

70

Fig.1 A schematic of the MD simulation system of SiO
2
(100) substrate and liquid decane at 350K

II. COMPUTATIONAL DETAILS

A. Molecular model

Mainly three kinds of models have been utilized to describe an alkane molecule for molecular
dynamic simulations, which include the all atom (AA) model [19], the united atom (UA) model [20]
and the anisotropic united atom (AUA) model [21]. In the UA model, each of CH
2
and CH
3
groups is
represented by a pseudoatomwith a spherical potential surface, which is connected to other
pseudoatoms to represent linear chain molecules. The AUA is a sort of UA, although in the AUA
model, the force center is moved away from the carbon for better accounting of interactions.The AA
models reproduce the molecular structure including hydrogen atoms and flexibility of molecules related
to them, although the computational time is significantly longer than the UA models.Mainly for
computational reasons, most of the researchers used UA in studies of alkane properties. In the present
work, we used a UA model to describe alkane molecules.From now on, we refer to the united
pseudoatoms as atoms.The NERD forcefield [16] was used to define intra- and intermolecular
interactions. In this force field, total potential energy of the system is written as the sum of nonbonded
interactions, bond bending, bond stretching and torsion potential. In the NERD force field, interaction
between two atoms which are located more than three atoms apart on the same molecule and atoms
located on the differentmolecules are given by the Lennard-Jones (LJ) 12-6 potential.

( )
12 6
LJ
4
ij ij
ij ij
ij ij
U r
r r

(
| | | |
(
= | |
| |
(
\ \

(1)

where
ij
r is the distance between atoms i and j. The energy parameters for the methyl and methylene
groups are
3
21
CH
1.4358 10 J

= and
2
22
CH
6.3233 10 J,

= respectively. The size parameter of CH
3
and CH
2

units are
3
CH
3.91 = and
2
CH
3.93 = respectively. Interactions between two different sites are
described by the standard Lorentz-Berthelot combining rules.

ij ii jj
= and
2
ii jj
ij

+
= (2)

The bond bending, bond stretching and torsion are the deformations defined by other interaction
potential functions included within the chains. The bending takes place between any three neighbor
atoms within a molecule and is modeled by the harmonic potential
71

Position-z(A)
D
e
c
a
n
e
n
u
m
b
e
r
d
e
n
s
i
t
y
(
m
-
3
)
S
i
l
i
c
a
n
u
m
b
e
r
d
e
n
s
i
t
y
(
m
-
3
)
0 50 100 150
2E+28
4E+28
6E+28
5E+28
1E+29
1.5E+29
2E+29
2.5E+29
Decane
Silica
350K

Fig.2 Number density distribution of-quartz/decane syatem at 350K.

( ) ( )
2
0
1
2
U k
=
(3)
where is the bond angle. The constant k
is 8.629110
19
J/rad
2
and equilibrium angle
0
is
o
114.0 .

The bond stretching potential is given as follows
( ) ( )
2
eq
2
r
ij ij
k
U r r b =
(4)

where
r
k is 1.332310
18
J/
2
and b
eq
is 1.54. The torsion occurs between any four neighboring atoms
in a molecule. The torsion potential that works between two atoms which are two atoms apart is defined
by the following function.

( ) ( ) ( ) ( )
0 1 2 3
1 cos 1 cos2 1 cos3 U V V V V = + + + + +
(5)
where is the dihedral angle, and V
0
=0 J, V
1
=4.901810
21
J, V
2
= 9.414610
22
J and V
3
=
1.092510
20
J.

In the present work we modeled the -quartz wall using the force field of Lopes et al. [3]. This
is an optimized CHARMM potential for -quartz. In this force field, total potential energy is comprised
of bond stretching, bond bending, torsion, electrostatic and Lennard-Jones interaction. Silicon, oxygen
and hydrogen are treated as interaction sites. For the potential parameters for the silica please refer to
Lopes et al. [3].

B. Computational systems

To examine the structure of alkanes in the vicinity of -quartz surfaces we have performed the
molecular dynamics study. Fig.1 shows an example of the simulation system. System consists of a pair
of -quartz solid walls and a liquid alkane is sandwiched between solid walls. The -quartz solid wall
was created in such a way that 100 plane was perpendicular to the z-axis. The surface of the left wall
was terminated by OH (silanol) and the right wall by H (silane). In this study, (100) crystal plane was
used for the solid surface, and these surface was OH- or H-terminated, which gives hydrophilic and
hydrophobic characteristics, respectively. There are generally two types of silanol (-OH) termination;
one is called germinal silanol which has two OH groups bonded to a Si atom. The other one is called
vicinal silanol which has one OH group bonded to a Si atom and forms a hydrogen bond with the
72

adjacent silanol groups. Periodic boundary conditions were applied in three spatial directions. A liquid
film is enclosed in a box of lengths L
x
=29.4, L
y
=31.8 and L
z
=150 for decane, L
x
=49.1,L
y
=53.0
and L
z
=150 for tetracosane. The LJ and coulomb interactions were truncated with a cut-off radius
(r
c
)of12.0 . The time integration of equations of motion is implemented by the reversible reference
system propagator algorithm (r-RESPA) method [22]with multiple time scales (MTS). An integration
time step of 1fs for the intermolecular motion and 0.2fs for the intramolecular motion were used in all
simulations. Initially, liquid densities of alkanes at three temperatures examined were calculated from
bulk liquid simulations. Next, initial configuration was created by placing the required number of
molecules randomly in between the two -quartz solid walls so as to have the saturated liquid pressure
in the direction normal to the film. After that, the system temperature was gradually raised to the
required temperature and then simulations were performed for NVT ensemble, i.e. with constant
number of particles, volume and temperature for 510
6
intermolecular time steps. The simulation
system was maintained at constant temperatures using Nose-Hoover thermostat. Equilibrium averages
were collected for about 2 ns.
Position-z (A)
D
e
n
s
i
t
y
(
k
g
/
m
3
)
0 50 100 150
0
500
1000
1500
T=350K
T=400K
T=450K
o
Decane

(a)
Position-z(A)
D
e
n
s
i
t
y
(
k
g
/
m
3
)
0 50 100 150
0
500
1000
1500
T=400K
T=450K
T=500K
Tetracosane
o

(b)

Fig.3 Density distribution along z direction for (a) decane at T=350 K, 400K and 450K (b) tetracosane at
T=400K, 450K and 500K
73

III. RESULTS AND DISCUSSION

All quantities were calculated after the system has reached equilibrium and interface has been
formed. The density profile is one of the fundamental properties that represent the structure of the
interface region. The local density was obtained by dividing the rectangularparallelepiped simulation
box into slabs with a thickness of0.1 in z direction.Time-averagednumber density of atoms of decane
molecules and -quartz system at 350K is shown in Fig. 2.Where -quartz density is shown in dashed
line and decane density is shown solid line. Time-averaged densityprofiles of decane are characterized
by oscillation in the vicinity of -quartz substrate. The amplitude ofpeaks is related to the order of
molecules at the interface.In adsorption layer, liquid molecules are adsorbed to solid a surface, which
isdescribed by the first peak in the density profile.If we observe the regions closely near the interfaces,
a very slight overlap exists between number densities of solid and liquid molecules. This implies that
very small amount of decane molecules get into the voids on the solid walls.When compared with
hydrophilic surface, larger number of molecules gets into the hydrophobicsurface.From now on,
density distributions and distributions of the orientation order parameter are presented only for the
portions of the liquidsto study the structure of liquid in the vicinity of -quartz. Density profiles for
decane at T=350K, 400K and 450K, and tetracosane at T=400K, 450K, and 500K are shown in Fig. 3.
The density profilesexhibit a flat region of a well-equilibrated bulk liquid phase away from the surface
of the -quartz walls.The amplitude of oscillations decreases when moving away from the wall and
disappears after some distance. As expected, Fig.3 shows that with an increase in temperature, liquid
densitydecreases.At 350Kheight of the first peak of the densityprofile ishighernearhydrophilic side than
the hydrophobic side for decane. The heights of the first peaks of the density profile near hydrophilic/
hydrophobic surfacesare sameat 400K.The decay of oscillation occurs in a similar manner when we
compare decane and tetracosane at the same temperature. For a particular alkane, location of the first
peak is slightly moved away from the surface with an increase in temperature. Heights of the peaks in
the density profile are dependent on the temperature. It is also observed that distance between
neighboring peaks is marginally depends on temperature. As temperature goes higher, density
fluctuations far away from the wall are not prominent.

The orientation order parameter can be used to quantify the effect of interface on the chain
ordering. A convenient orientation order parameter is defined as follows [5]

2
1
( ) 3cos 1
2
P z =
(6)

where is the angle between a vector connecting two carbon atoms which are two units apart in
a molecule and interface normal. The average is taken over all vectors and time steps. The range of
this parameter is [-0.5, 1]. A positive value indicates preferential alignment normal to the interface.
Negative value indicates preferential alignment parallel to the interface. Zero indicates completely
random arrangement of molecules. To calculate spatial distribution of the orientation order parameter,
the simulation box was divided into slabs with a width of 1 in z direction. A vector connecting
between two atoms is assigned to the slab where the midpoint between two atoms is located. Fig. 4
shows the average orientation order parameter in z direction. In Fig. 4 density profiles for decane and
tetracosane are shown as dash dotted lines at 350K and 400K. Approximate minimum orientation order
parameter is 0.4 in the adsorption layer near the OH-terminated side which indicates that molecules
are almost parallel to the interface. Molecules are less parallel to the interface in the adsorption layer
near the H-terminated surface. In the adsorption layer close to hydrophilic surface, orientation order
parameter is positive. That means a small portion of molecules in the first adsorption layer intrude into
the solid wall in perpendicular direction to the interface near the hydrophilic side. On the other hand the
intruded parts of the molecules near the hydrophobic side are parallel to the interface. This might be
because of the difference in topologyon the hydrophilic and hydrophobic-quartz surfaces. As expected,
the orientation order parameter shows zero in the bulk liquid region, which means molecules are
74

randomly oriented. The orientation ordering parameter is positive in between the layers adjacent to
hydrophobic/hydrophilic surfaces which mean molecules are perpendicular to the interface. This is a
sign of interlayer interdigitation[5].With an increase in temperature molecules are preferentially less
parallel/perpendicular to the interface in each internal layer. Both decane and tetracosane show similar
kind of ordering close to the hydrophobic and hydrophilic surfaces.

Position-z(A)
O
r
i
e
n
t
a
t
i
o
n
o
r
d
e
r
p
a
r
a
m
e
t
e
r
D
e
n
s
i
t
y
(
k
g
/
m
3
)
0 50 100 150
-0.4
-0.2
0
0.2
0.4
0.6
0
500
1000
1500
T=350K
T=400K
T=450K
Decane
o

(a)
Position-z(A)
O
r
i
e
n
t
a
t
i
o
n
o
r
d
e
r
p
a
r
a
m
e
t
e
r
D
e
n
s
i
t
y
(
k
g
/
m
3
)
0 50 100 150
-0.4
-0.2
0
0.2
0.4
0.6
0
500
1000
1500
T=400K
T=450K
T=500K
Tetracosane
o

(b)

Fig.4Orientation order parameter as a function of distance for (a) decane at T=350k,400K and
450K (b) tetracosane at T=400K, 450K and 500K
75

IV. CONCLUISIONS

We have investigated the molecular structure of liquid decane and tetracosane at different
temperaturesin the vicinity of (100) -quartz surfaces terminated by OH- and H- groups,which are
hydrophilic and hydrophobic surfaces, respectively.Time-averaged mass density profiles and ordering
parameter are analyzed at differenttemperatures. For all cases studied, averaged density profile along
z-direction consists of oscillations near the solid wall. Amplitudes of the fluctuations of the
time-averaged density profile are slightly depending on the temperature for decane and
tetracosane.Molecular orientation is investigated by examining the orientation order parameter. In the
adsorption layer close to the hydrophilic side molecule are more parallel to the interface than the
molecules in adsorption layer near hydrophobic surface. Alkane molecules are oriented randomly in
the bulk liquid region. Liquid molecular orientation is almost independent of thechain length of
molecule in the vicinity of-quartz surface.

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