Water cluster

Hypothetical (H2O)100 icosahedral water cluster and

the underlying structure.

In chemistry a water cluster is a discrete

hydrogen bonded assembly or cluster of
molecules of water.[1] These clusters have
been found experimentally or predicted in
silico in various forms of water; in ice, in
crystal lattices and in bulk liquid water, the
simplest one being the water dimer (H2O)2
. Shu et al. reported the images of water
clusters of 100 micrometres.[2][3] Ongoing
academic research is important because
the realization that water manifests itself
as clusters rather than an isotropic
collection may help explain many
anomalous water characteristics such as
its highly unusual density temperature
dependence. Water clusters are also
implicated in the stabilization of certain
supramolecular structures. So little is
understood about water clusters in bulk
water that it is considered one of the
unsolved problems in chemistry.

Theoretical studies (in-silico

structures)
In-silico (see: water models), cyclic water
clusters (H2O)n are found with n = 3 to
60.[4][5] Structures of water molecules with
the highest resolution have been
demonstrated in the studies of Richard
Saykally of Berkeley College of
Chemistry.[6] With increasing cluster size
the oxygen to oxygen distance is found to
decrease which is attributed to so-called
cooperative many-body interactions: due
to a change in charge distribution the H-
acceptor molecule becomes a better H-
donor molecule with each expansion of
the water assembly. Many isomeric forms
seem to exist for the hexamer: from ring,
book, bag, cage, to prism shape with
nearly identical energy. Two cage-like
isomers exist for heptamers, and
octamers are found either cyclic or in the
shape of a cube. Even larger clusters are
predicted: the fullerene-like cluster (H2O)28
is called the water buckyball and even for a
280 water molecule monster icosahedral
network (with each water molecule
coordinate to 4 others) there is found a
local energy minimum. The 280 molecule
icosahedral structure, which is 3 nm in
diameter, consists of icosahedral shells
with 280, 100 and 320 molecules (the 100
molecule structure is shown the figure
above).[7][8] There is increased stability
with the addition of each shell.[9] A look at
the recent scientific literature may reveal
good reviews on the studies of water
clusters employing ab initio
methods.[10][11] These clusters are also
important for studying hydration
phenomena at molecular level since they
form the basic building blocks of the
hydrated clusters.[12][13][14] There are
theoretical models of water clusters of
more than 700 water molecules by Martin
Chaplin and Stanislav Zenin.[15][16] They
have not been proven experimentally.

Experimental structures
Shu et al. observed water clusters under
microscope. The experiments were
conducted in two ways. One is making
sodium chloride solutions and sampling
water clusters from the solution and put
the solution with water clusters on a glass
slide under a microscope. The second
method is to put a drop of Milli Q water on
a glass slide under a microscope and put a
grain of salt next to the water drop then
push the salt grain inside the water drop.
Under the microscope salt starts to
dissolve and break into smaller salt
particles. Some of the salt particles enter
water clusters and reveals the appearance
of water clusters.

The experimental observation[17][18] of

water clusters requires sophisticated
spectroscopic tools such as Far-infrared
(FIR) vibration-rotation-tunneling (VRT)
spectroscopy (an infrared spectroscopy
technique). With water trapped in a liquid
helium environment the hexamer is found
to be a cyclic planar assembly but in the
gas-phase the cage is found and in an
organic host (water trapped in the crystal
lattice of an organic compound) a
conformation reminiscent of a
cyclohexane chair conformation.
Experiments combining IR spectroscopy
with mass spectrometry reveal cubic
configurations for clusters in the range W8-
W10.

When the water is part of a crystal

structure as in a hydrate, x-ray diffraction
can be used. Conformation of a water
heptamer was determined (cyclic twisted
nonplanar) using this method[19]. Further,
multi-layered water clusters with formulae
(H2O)100 trapped inside cavities of several
polyoxometalate clusters were also
reported by Mueller et. al.[20].[21].

Experimental study of any supramolecular

structures in bulk water is difficult
because of their short lifetime: the
hydrogen bonds are continually breaking
and reforming at the timescales faster
than 200 femtoseconds.[22]

Bulk water models

According to the so-called in silico method
quantum cluster equilibrium (QCE) theory
of liquids W8 clusters dominate the liquid
water bulk phase followed by W5 and W6
clusters. In order to facilitate a water triple
point the presence of a W24 cluster is
invoked. In another model bulk water is
built up from a mixture of hexamer and
pentamer rings containing cavities
capable of enclosing small solutes. In yet
another model an equilibrium exists
between a cubic water octamer and two
cyclic tetramers. However, in spite of
much model-making, no model yet has
reproduced the experimentally-observed
density maximum.[23][24]

See also
Hydrogen bond
Mpemba effect
 Richard J. Saykally
Water (properties)

References
1. Ralf Ludwig (2001). "Water: From
Clusters to the Bulk". Angew. Chem. Int. Ed.
40 (10): 1808–1827. doi:10.1002/1521-
3773(20010518)40:10<1808::AID-
ANIE1808>3.0.CO;2-1 . PMID 11385651 .
2. Shu, L., Obagbemi, I. J., Jegatheesan, V.,
Liyanaarachchi, S., Baskaran, K. (2015)
Effect of multiple cations in the feed
solution on the performance of forward
osmosis, Desalination and Water
Treatment, Vol. 54, pp845-852.
3. Shu, L., Wu, S., Jegatheesan, V. (2013)
Directly observe sodium chloride
aggregates waltzing through dilute
solutions, in ed., Shu, L., Jegatheesan, V.,
Pandey, A. Virkutyte, J., Djati Utomo, H.
Solutions to Environmental Challenges
through Innovation in Research, Asiatech,
New Delhi. ISBN 81-87680-31-8.
4. Fowler, P. W., Quinn, C. M., Redmond, D.
B. (1991) Decorated fullerenes and model
structures for water clusters, The Journal
of Chemical Physics, Vol. 95, No 10, p.
7678.
5. Ignatov, I., Mosin, O. V. (2013) Structural
Mathematical Models Describing Water
Clusters, Journal of Mathematical Theory
and Modeling, Vol. 3, No 11, pp. 72-87.
6. Keutsch, F. N. and Saykally, R. J. (2001)
Water clusters: Untangling the mysteries of
the liquid, one molecule at a time, PNAS,
Vol. 98, № 19, pp. 10533–10540.
7. Tokmachev, A.M., Tchougreeff, A.L.,
Dronskowski, R. (2010) Hydrogen-Bond
Networks in Water Clusters: An Exhaustive
Quantum-Chemical, European Journal of
Chemical Physics And Physical Chemistry,
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8. Sykes, М. (2007) Simulations of RNA
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22. Smith, Jared D.; Christopher D. Cappa;
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Geissler; Richard J. Saykally (2005).
"Unified description of temperature-
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23. Borowski, Piotr; Jaroniec, Justyna;
Janowski, Tomasz; Woliński, Krzysztof
(2003). "Quantum cluster equilibrium theory
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24. Lehmann, S. B. C.; Spickermann, C.;
Kirchner, B. (2009). "Quantum Cluster
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Water clusters at London South Bank
University Link
The Cambridge Cluster Database -
Includes water clusters calculated with
various water models and the water
clusters explored with ab initio
methods .
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