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Behavior of Water Dimer Under The Influence of External Electric Fields
Behavior of Water Dimer Under The Influence of External Electric Fields
A detailed quantum chemical study has been carried out at the CCSD(T) level of theory to understand the behavior of
water dimer under the influence of external electric fields. The energy values obtained at this level of theory follow the same
trend as observed with the DFT and MP2 levels of theory. Our calculations show that water dimer gets stabilized with
increase in the strength of electric field. A slight increase in the hydrogen bond distance and relatively larger decrease in the
hydrogen bond angle is found with the increase in the strength of electric field. The dipole moment and HOMO-LUMO
energy gap increase with the increase in the strength of electric field.
Keywords: Water dimer, Electric field, Coupled cluster methods, Dipole moments, HOMO-LUMO energy gap
Water clusters are group of water molecules (ranging other hand, quantum chemical calculations16-19
from two to a few) that are held together by hydrogen employing very high level of theory have been
bonds. Unlike atoms and molecules and solids, the used to describe the interactions of small size clusters
properties exhibited by the clusters under the (n < 20) to get accurate numbers for the observables
influence of external field are unique in many ways. It like stabilization energy, dipole moment, etc., which
is important to study water clusters in order to further help in better understanding of the physics
understand properties of the bulk water, cloud and involved.
ice formation, solution chemistry, electrochemical Girardi and Figueiredo5 in their square model water
and biochemical processes. To get an insight into showed that the number of hydrogen bonds per molecule
water clusters, it is necessary to know its behavior is a monotonic decreasing function of the field
under external influences, in particular, in the magnitude. In 1991, Zhu et al.6 studied the effect of an
presence of electric field. Various methods used intense laser field on liquid water using classical
for understanding the interaction of water molecules molecular dynamics simulations using a water model
like new laser spectroscopy experiments, combined SPC-FP. They showed that both the liquid structure and
with the global analysis of potential surfaces and intramolecular geometry get distorted by forming a large
diffusion Monte-Carlo methods are explained in number of bifurcated hydrogen-bonds. Suresh et al.7
the previous reports.1,2 developed a theory based on reaction equilibria and
Several attempts have been made by researchers to Boltzman distribution for studying hydrogen-bond
understand the effect of external electric field on network of water in external electric field and predicted
water, both experimentally1-4 and theoretically.5-23 For that at practically attainable field strengths, the electric
ease of understanding, the studies have been field cannot disrupt the hydrogen-bond network.
segregated into two groups on the basis of the number However, weakening of the bonds is observed at higher
of water molecules involved. Water clusters (H2O)n in field strengths which cannot be attributed to the effect of
which n ≤ 20 comprise one group and the ones electric field alone. Very recently Saitta et al.8 studied
containing more than 20 water molecules fall in the liquid water using ab initio molecular dynamics and
other. In the literature, we find that molecular observed (i) significant modification in the hydrogen-
dynamics simulations have been carried out in order bond length and molecular orientation at low-to-
to explain the bulk water and liquid water which moderate fields, and, (ii) dissociation and ionic current at
involve more than 20 molecules of water.10-15 On the high fields (above 0.35 V/Å). A number of studies on
MONDAL et al.: WATER DIMER IN EXTERNAL ELECTRIC FIELDS 1057
bulk water using molecular dynamics is available which value, the three-dimensional structure of clusters
focus on structural modification by external electric opens up and forms linear, branched or net-like
field.9-15 The molecular dynamics simulations, in structures such that dipolar water monomer align in
general, suggest that the structure of water (bulk, liquid direction of electric field. Results for octamer are also
and clusters) changes after a particular threshold electric found to be consistent with those of James et al.20
field, which is higher for clusters when compared to that In each case, the threshold values depend on size
for the bulk or liquid water. of the cluster. Toledo et al.24 have investigated
At this juncture, we would emphasize on the the effect of external electric field on water clusters
literature pertaining only to the clusters containing less n = 2–16 using DFT and noticed a change in
than 20 water molecules. Dykstra16 using a model the number of hydrogen-bonds, thereby leading to
potential found that in a weak field, minor distortions reduction in cluster sizes having stronger inter-cluster
in trimer cyclic structure occurs, whereas at very high hydrogen bonds.
field (~0.08 a. u.) the trimer ring opens since the field From the available literature, Karahka and
overcomes the intermolecular interaction. A DFT based Kaeuzer17 made some generalizations regarding the
study by Karahka and Kreuzer17 showed that for small field effects on water clusters, as follows: (a) at low
external electric fields the water whiskers polarize and fields, only “physical effects” such as polarization of
align along the field. The alignment of dipole moment the atoms and molecules occur, and, (b) the high
with the field is favoured because of the formation of fields are responsible for the alterations in the
staggered conformation (in this case, helical) which is chemical characteristics of atoms and molecules.
usually lower in energy. At high fields, charge- In the present work, we explore and analyze
transfer and re-hybridization leading to closing of the systematically the effect of external static electric
HOMO-LUMO gap is observed which finally results field on the electronic properties of water dimer in the
in fragmentation. Acosta-Gutiérrez et al.18 carried out ground state using CCSD(T) level of theory25 which is
molecular dynamics simulation with TIP4P and the “gold standard in quantum chemistry”.
polarizable Dang-Chang potential to study the global
minimum structure, energy, dipole moment of water Methodology
cluster (n ≤ 20) in low and moderate electric fields All calculations were performed using the
(E< 0.6 V/Å). They observed two distinct transitions GAUSSIAN’03 package.26 The structure
in the electric field: (i) field range of 0.1–0.3 V/Å, in optimization, with and without electric field,
which the hydrogen bond reorganizes, and, (ii) field for water dimer were carried out under the second
range of 0.3–0.5 V/Å in which elongation of cluster in order Moller-Plesset perturbation (MP2)27 level of
direction of electric field occurs with enhanced dipole theory employing the 6-311++G** basis set. Then
moments. For large enough fields (0.6–1 V/Å), the the single point calculations for the MP2 theory
larger structures (n > 10) converges to helical optimized geometries (with and without electric field)
structures. Choi et al.19 have investigated small water were performed at the CCSD(T) level of theory.
clusters (n = 3–5) in external electric field employing
DFT and concluded that with increasing electric field, Results and Discussion
the clusters open up to form a linear chain along the The optimized geometries and the energy values
direction of the field. Their results compare well with for the corresponding equilibrium geometries without
those of James et al.20, who showed the change of any external perturbation for the monomer, dimer,
structure of water clusters from compact to more trimer and its higher oligomers (4 ≤ n ≤ 20) calculated
extended structures at higher fields, employing at a higher levels of theory (MP2 and DFT) can be
classical rigid-body models of the TIPnP (n = 3–5) found elsewhere.28-31 Herein we have calculated the
family of effective pair potentials. Similar results are energies corresponding to the equilibrium geometries
reported for small methanol clusters, in terms of effect of water dimer. The initial geometry is optimized in
of enhanced electric field on structure, although the absence of field and this value is reported as the
threshold field is slightly higher for cyclic clusters of energy at zero field or field-free energy. To study
methanol.21 Rai et al.22,23 have studied water clusters the effect of electric field, the field is applied in the
for n = 6–8 and n = 9–20 using DFT and found that OH–O hydrogen bond direction as shown in Fig. 1
due to applied electric field above a certain threshold and the structure of the dimer is optimized in the
1058 INDIAN J CHEM, SEC A, AUG-SEPT 2013