Likely candidates for the global potential energy minima of (H$_{2}$O)$_{n}$ clusters with $n\leq21$ on the (0001)-surface of graphite are found using basin-hopping global optimization. The potential energy surfaces are constructed using the TIP4P intermolecular potentials for the water molecules (the TIP3P is also explored as a secondary choice), a Lennard-Jones water-graphite potential, and a water-graphite polarization potential that is built from classical electrostatic image methods and takes into account both the perpendicular and parallel electric polarizations of graphite. This potential energy surface produces a rather hydrophobic water-graphite interaction. As a consequence, the water component of the lowest graphite-(H$_{2}$O)$_{n}$ minima is quite closely related to low-lying minima of the corresponding TIP4P (H$_{2}$O)$_{n}$ clusters. In about half of the cases the geometrical substructure of the water molecules in the graphite-(H$_{2}$O)$_{n}$ global minimum coincides with that of the corresponding free water cluster. Exceptions occur when the interaction with graphite induces a change in geometry. A comparison of our results with available theoretical and experimental data is performed.
Deep Dive into Global Potential Energy Minima of (H$_{2}$O)$_{n}$ Clusters on Graphite.
Likely candidates for the global potential energy minima of (H$_{2}$O)$_{n}$ clusters with $n\leq21$ on the (0001)-surface of graphite are found using basin-hopping global optimization. The potential energy surfaces are constructed using the TIP4P intermolecular potentials for the water molecules (the TIP3P is also explored as a secondary choice), a Lennard-Jones water-graphite potential, and a water-graphite polarization potential that is built from classical electrostatic image methods and takes into account both the perpendicular and parallel electric polarizations of graphite. This potential energy surface produces a rather hydrophobic water-graphite interaction. As a consequence, the water component of the lowest graphite-(H$_{2}$O)$_{n}$ minima is quite closely related to low-lying minima of the corresponding TIP4P (H$_{2}$O)$_{n}$ clusters. In about half of the cases the geometrical substructure of the water molecules in the graphite-(H$_{2}$O)$_{n}$ global minimum coincides wit
arXiv:0706.1152v1 [physics.atm-clus] 8 Jun 2007
Global
P
oten
tial
Energy
Minima
of
(H2
O)n
Clusters
on
Graphite
B.
S.
González,
J.
Hernández-Ro
jas,
J.
Bretón,
and
J.
M.
Gomez
Lloren
te∗
Departamen
to
de
Físi a
F
undamen
tal
I
I
Univ
ersidad
de
La
Laguna,
38205
T
enerife,
Spain
Septem
b
er
5,
2021
Abstra t
Lik
ely
andidates
for
the
global
p
oten
tial
energy
minima
of
(H2
O)n
lusters
with n ≤21
on
the
(0001)-surfa e
of
graphite
are
found
us-
ing
basin-hopping
global
optimization.
The
p
oten
tial
energy
surfa es
are
onstru ted
using
the
TIP4P
in
termole ular
p
oten
tials
for
the
w
a-
ter
mole ules
(the
TIP3P
is
also
explored
as
a
se ondary
hoi e),
a
Lennard-Jones
w
ater-graphite
p
oten
tial,
and
a
w
ater-graphite
p
olar-
ization
p
oten
tial
that
is
built
from
lassi al
ele trostati
image
meth-
o
ds
and
tak
es
in
to
a oun
t
b
oth
the
p
erp
endi ular
and
parallel
ele tri
p
olarizations
of
graphite.
This
p
oten
tial
energy
surfa e
pro
du es
a
rather
h
ydrophobi
w
ater-graphite
in
tera tion.
As
a
onsequen e,
the
w
ater
omp
onen
t
of
the
lo
w
est
graphite-(H2
O)n
minima
is
quite
losely
related
to
lo
w-lying
minima
of
the
orresp
onding
TIP4P
(H2
O)n
lus-
ters.
In
ab
out
half
of
the
ases
the
geometri al
substru ture
of
the
w
a-
ter
mole ules
in
the
graphite-(H2
O)n
global
minim
um
oin ides
with
that
of
the
orresp
onding
free
w
ater
luster.
Ex eptions
o
ur
when
the
in
tera tion
with
graphite
indu es
a
hange
in
geometry
.
A
om-
parison
of
our
results
with
a
v
ailable
theoreti al
and
exp
erimen
tal
data
is
p
erformed.
∗
Correp
onding
author.
E-mail
addr
ess
:
jmgomez ull.es
1
1
In
tro
du tion
The
in
tera tion
of
arb
ona eous
materials
su
h
as
fullerenes,
arb
on
nan-
otub
es
and
graphite
with
atoms
and
mole ules
share
man
y
prop
erties.
In
parti ular,
in
this
w
ork
w
e
will
b
e
on erned
with
the
in
tera tion
b
et
w
een
w
ater
and
graphite.
A
deep
understanding
of
the
features
and
prop
erties
of
this
in
tera tion
is
of
parti ular
in
terest
in
te
hnologi al
appli ations,
su
h
as
those
related
with
the
use
of
w
ater
as
a
lubri an
t
for
graphite
[1
,
2℄,
and,
more
indire tly
,
in
the
b
eha
vior
of
w
ater
at
the
nanometer
s ales
when
material
related
to
graphite,
su
h
as
arb
on
nanotub
es,
are
presen
t.
W
ater-graphite
in
tera tion
is
also
relev
an
t
in
the
design
of
orrosion-free
om
bustion
ham-
b
ers
and
ro
k
et
nozzles,
sin e
w
ater
is
a
univ
ersal
om
bustion
pro
du t
and
graphite
is
an
imp
ortan
t
surfa e
material
b
e ause
of
its
hemi al
inertness
under
extreme
onditions
[3℄.
Other
elds
b
ene ting
from
this
kno
wledge
in lude
the
en
vironmen
tal
s ien es
[4℄
and
astroph
ysi s
[5
℄,
sin e
graphite
is
a
go
o
d
andidate
for
the
omp
osition
of
nano
parti les
and
dust
grains.
Despite
the
natural
abundan e
of
w
ater
and
graphite,
relativ
ely
few
exp
er-
imen
tal
data
are
a
v
ailable
for
their
in
tera tion.
Studies
at
lo
w
temp
erature
(T = 85
K)
and
lo
w
o
v
erage
using
temp
erature
programed
desorption
and
vibrational
high
resolution
ele tron
energy
loss
sp
e tros op
y
ha
v
e
sho
wn
that
w
ater
is
adsorb
ed
non
disso
iativ
ely
on
the
graphite
surfa e
forming
h
ydro-
gen
b
onded
aggregates
with
a
t
w
o
dimensional
stru ture
that
hanges
in
to
a
three
dimensional
one
up
on
w
arming
[6℄.
The
w
ater
arrangemen
t
for
the
2
t
w
o-dimensional
stru ture
is
unkno
wn,
as
is
also
unkno
wn
the
role
pla
y
ed
b
y
small
w
ater
lusters
in
the
gro
wth
of
these
stru tures.
Exp
erimen
tal
information
ab
out
the
w
ater-graphite
binding
energies
and
stru tural
asp
e ts
is
urren
tly
la
king
ev
en
for
the
w
ater-monomer
adsorp-
tion.
T
o
our
kno
wledge,
there
are
only
the
early
w
ater-graphite
binding
energy
b
y
Kieslev
et
al.
(15.0
kJ/mol)
[7℄
and
the
more
re en
t
asso
iation
energy
rep
orted
b
y
Kasemo
et
al.
[6℄.
In
the
last
few
y
ears
some
results
from
theoreti al
al ulations
ha
v
e
b
een
made
a
v
ailable.
Some
of
these
studies
are
on erned
with
ma ros opi
fea-
tures
of
the
w
ater-graphite
in
tera tion.
In
this
group
w
e
an
in lude
the
w
ork
b
y
W
erder
et
al.
[8℄,
who
t
an
in
tera tion
p
oten
tial
form
to
exp
erimen
tal
data
for
the
on
ta t
angle
of
w
ater
nano
droplets
on
graphite
surfa es.
A
similar
s
heme
is
used
b
y
P
ertsin
et
al.
to
sim
ulate
lubri an
t
prop
erties
from
a
w
ater-graphite
in
tera tion
that
w
as
previously
tted
to
ab-initio
[9℄
and
empiri al
data
[10℄.
Finally
Gati a
et
al.
ha
v
e
used
empiri al
w
ater-graphite
p
oten
tials
to
lo
ok
for
a
w
etting
transition
[11℄.
A
b
initio
al ulations
ha
v
e
b
een
re en
tly
rep
orted.
By
using
se ond-order
Möller-Plesset
p
erturbation
theory
,
F
eller
et
al.
[12℄
ha
v
e
pro
vided
the
in
ter-
a tion
energy
b
et
w
een
a
w
ater
mole ule
and
a enes
as
large
as
C96
H24
;
the
v
alue
of
24
kJ/mol
that
w
as
obtained
for
this
energy
seems
to
b
e
unph
ysi ally
high
[13
℄.
This
on lusion
is
on rmed
b
y
the
re en
t
theoreti al
al ulations
b
y
Sudiarta
and
Geldart
[14℄.
Using
the
same
Möller-Plesset
s
heme
for
a
w
ater
mole ule
on
b
o
…(Full text truncated)…
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