http://chemistry.berkeley.edu/news/saykally-continues-quest-for-water
by Michael Barnes
For a simple compound that is central to almost every
aspect of our existence, water remains fiendishly difficult to understand. No
one appreciates this better than chemistry professor Rich Saykally, who has
devoted many years to studying water.
Even
a minute sample contains far too many atoms and bonds to study, so Saykally has
explored water from the bottom up, first by creating clusters of just two
molecules and working up to larger and larger clusters.
In
an article in the June 3 issue of Science magazine,
Saykally and co-workers characterize the water octamer, a cluster of eight
water molecules in a roughly cubic form. Says Saykally, “Understanding the
octamer is important because it represents a transition to structures formed by
stacking quasi-planar rings, a dominant pattern in larger systems. The water
octamer has become an important benchmark.”
A
huge effort has been devoted towards the development of computer models for
water that can correctly describe its structure and physical properties,
thermodynamics, phase behavior, solvation properties, and ultimately, its
chemistry.
“That
we still do not have such a robust computational approach for water, let alone
for aqueous solutions and aqueous interfaces, is a great impediment to science,”
Saykally notes.
While
isolated clusters do not exist as such in bulk water, highly detailed
spectroscopic study provides accurate benchmarks for characterization of the
complicated many-body forces that operate in bulk-water phases.
Graphic: The two cuboidal structures of the water octamer characterized by infrared and terahertz laser spectroscopy and theory. These cuboids are formed by stacking of two four-membered rings with the circular direction of the hydrogen bonds in the same (left) and opposite (right). Larger clusters form via a similar stacking of larger quasiplanar rings.
In
the Science paper, the Saykally lab has presented
the first high-resolution spectroscopic study of the water octamer. Terahertz
vibration-rotation-tunneling (VRT) spectroscopy was used for the measurements.
This work complements recent and elegant microwave spectroscopy characterization
of the water heptamer and nonamer, also published in Science.
The octamer could not be detected by that method because it lacks a dipole
moment.
Nearly
100 individual measurements were made with parts-per-million accuracy and
fitted to a standard model, which characterizes the structures and vibrational
distortions of the cluster. Two distinct cuboidal structures were characterized
via measurement of their torsional vibrations. The results are in good
agreement with recent theoretical predictions of the hydrogen-bond
rearrangement tunneling rates and octamer cluster structures.
Considerable
progress has been realized over the last several years by the Saykally group
and their collaborators in the long-sought quest for a universal first-principles
model of water. This goal has been aided by the development of several new
potential energy surfaces, including new spectroscopically refined surfaces.
“Our
approach is to help develop, test, and refine potential energy surfaces via our
VRT spectroscopy results for water clusters, in combination with
state-of-the-art theoretical calculations,” says Saykally.
It
is important to continue these efforts in order to realize the ambitious but
crucial goal of producing a water model that is relatively simple, yet capable
of accurately reproducing and predicting observable properties of water in all
of its forms (including the liquid-vapor interface) over large ranges of
conditions. That is the goal that Saykally continues to pursue.
