Sustainable energy: how quantum chemistry can help
F. De Angelis, S. Fantacci, R. Gebauer, Journal of Physical
Sustainable energy: How quantum chemistry can help
Computer simulations of electronic and structural properties can give detailed insight into atomic-scale processes in functional materials. Such studies play an important role in the quest for better strategies to harvest and store renewable energy.
Osis. According to BP's 2011 Statistical by greatly increasing the use of renewable energy
ne of the biggest challenges for science and Renewable Energy
engineering today is the global energy cri- One possible way to address this looming energy crisis is
Review of World Energy , the worldwide sources like wind, hydro or solar energy. Amongst all
primary energy consumption in 2010 was 503 × 1018 J, those sustainable energy sources, by far the largest
which corresponds to an average energy consumption resource is the sun. In one hour, about 430 × 1018 J of
rate of 16 terawatt (TW). Most of this energy is obtai- solar energy strike the earth, a quantity which is
companed from fossil fuels, with roughly equal parts of oil, rable to all the energy which the world is currently
coal, and natural gas. Rapid growth of the global popu- consuming in one year. In spite of such a great potential,
lation and per capita energy consumption will lead to a only a very small fraction of today's energy is provided by
considerable projected increase in energy consumption the sun, mostly in the form of fuels from biomass. Two
during the next decades. Under moderate assumptions main reasons for the low utilization of the sun's potential
the world energy consumption rate can be forecast to are the prohibitively large cost of current photovoltaic
roughly 28 TW in 2050 . Such an increase of the pro- technologies and the intermittent nature of sunshine.
jected energy consumption is in stark contrast with the e issue of the high cost of photovoltaic electricity is
genediminishing availability of affordable fossil fuels. e rally recognized as a major hurdle for the widespread use of
drastic increase of oil and coal prices in recent years this technology. Traditional photovoltaic panels are usually
show that the current consumption rate of fossil fuels is based on silicon p-n junctions or on thin films of CdTe, a
pushing the possible extraction rates to its limits. semiconductor.Such panels have seen a strong reduction in
Moreover, the menace of climate change due to the price in recent years, mainly due to mass production and
ever-increasing levels of CO2 in the atmosphere calls for the availability of large quantities of pure silicon as raw
a drastic reduction in our use of fossil fuels. material. In spite of such progress, the adaptation of this
of a dye molecule
fe aTur eS SuSTainable ener gY
f ig. 1:
representation of a
solar cell. Solar
creates an electronic
excitation in dye
are attached to
the surface of a
excitation might be
from the dye's
(Homo) to its
orbital (l umo).
manifold of the
used to restore
on the dye and
with the second
technology is still dependent on public subsidies like
guaranteed feed-in tariffs for renewable electricity.
e issue of intermittency is less publicly discussed, but is
equally important. If renewable energy sources are to
provide a considerable fraction of the world's energy, then they
must be available whenever demand is high. is necessity
leads to the requirement of affordable energy storage. For
many applications like transport, such storage should also
provide a high volumetric and gravitational energy density.
All these challenges related to the conversion and
storage of energy are currently the focus of many research
efforts around the world. e interdisciplinary nature of
the issues calls for strong collaboration among experts
from diverse fields of science: basic physics to biology,
chemistry, materials science and engineering.
Amongst these fields, chemistry holds the center stage,
since progress in the development of a new device
must be accompanied by the design and synthesis of
corresponding functional materials. But within the field
of chemistry itself, collaborations between theorists and
experimentalists are crucial for the successful
development of such materials. For example, computer
simulations of the atomistic and electronic structure of
a new compound can lead to a clearer understanding
of the key processes which underlie the functioning of
a device. Insight on the atomic scale is therefore the
first step to a targeted improvement of materials.
An area where research has led to strong progress
recently is the field of so-called dye-sensitized solar cells
(DSSCs).A DSSC captures light using dye molecules that
strongly absorb in the visible frequency range. ese dye
molecules are attached to the surface of a wide-bandgap
semiconductor (oen TiO2). In contrast to traditional
solar cells, where the light absorption happens inside the
semiconductor, the wide-bandgap material in a DSSC
cannot directly harvest solar photons. Instead, the dye
molecules act like antennas that capture the sunlight.
Following photo-absorption, the excited electron is quickly
transferred to the conduction band of the semiconductor
from where it is led to an electrode. e hole that the
electron leaves behind on the dye molecule is filled from an
electrolyte surrounding the semiconductor. e
electrolyte is in contact with a second electrode used to close the
electrical circuit. is design of a DSSC is depicted
schematically in Fig. 1.
Such "third generation" photovoltaic devices do not
require ultra-pure, defect-free materials that are
expensive to obtain. Dye molecules and the DSSCs can be
produced using traditional "wet chemistry" methods. e
prospect of low-cost production methods and abundant
raw materials are the attractive features of third
generation devices. Moreover, efficiencies of up to 11% have
been reported for DSSCs. Nevertheless, much research is
still needed to improve this technology and make it a
viable alternative to standard solar cells.
eoretical modeling can intervene at various levels in
DSSCs. Firstly, the optical absorption properties of the
dye molecules themselves can be computed. eoretical
spectroscopy has always been a core discipline of
quantum chemistry. When new dye molecules are
considered, preliminary quantum chemical studies can
help identify promising candidate molecules. While the
synthesis of a new dye can take several months and
require well-equipped laboratories, a theoretical
spectrum can be obtained within hours, long before the
molecule in question has even been produced. In other
cases, researchers might consider various ligands to
enhance the optical properties of a given molecule. Also
in those cases, the availability of computed absorption
spectra can guide the choice of ligands.
A second area of theoretical interest is the interaction of
the dye molecules with the surface atomic structure.
Molecular dynamics simulations can reveal the
preferred adsorption sites of molecules and give information
about the stability of alternative adsorption geometries.
e presence of a liquid electrolyte further complicates
the situation. Computer simulations can shed light on
the role of the electrolyte in the stability of surface
structures and dye adsorption. In Fig. 2 an example is
shown where the interaction with liquid water leads to
the desorption of a dye from a TiO2 surface .
Particular theoretical focus has been drawn to the injection
of the excited electron from the dye into the conduction
band manifold of the semiconductor. e time scale of
this process is a very important factor determining the
efficiency of the device: if the injection process is slow, the
excited electron can de-excite radiatively or thermally
towards its ground state and the corresponding energy is
lost. Quantum mechanical computations have shown that
in some systems the interaction between the excited state
on the dye and the semiconductor is strong enough so that
the electron injection can occur in a few femtoseconds.
is is much faster than typical atomic vibrations, which
might lead to alternative de-excitation mechanisms.
Moreover, in this case, theoretical insight into the factors
determining the injection time can lead to a more
targeted choice of surface - dye couples .
One possibility to store the energy of intermittent
renewable sources is to convert the energy into chemical bonds.
Using CO2 and water as raw materials, an artificial
photosynthetic system might produce hydrocarbons that can be
easily stored and transported.Various routes to such a
system are currently examined. e approaches range from
genetically modified forms of algae or bacteria up to
electro-catalytic systems where (renewable) electricity is used
to produce chemical fuels. One important step in such
catalytic processes is the oxidation of water to produce the
electrons and protons needed to reduce CO2 to a fuel, as
shown schematically in Fig. 3.
e oxidation of water leading to the formation of one
oxygen molecule involves four electrons.An efficient
catalyst to drive this electrochemical reaction should be such
that each one of the four distinct electron transfer steps
occurs at nearly the same cost of energy. is is a rather
demanding requirement since each step involves
chemical species with very distinct oxidation states. Interestingly,
nature has managed to satisfy this requirement nearly
perfectly in the oxygen-evolving complex of photosystem II
. Man-made catalysts, however, suffer from the
necessity to apply so-called over-potentials that reduce the
efficiency of the water splitting .
Quantum chemical simulations can shed light on the
involved energy levels and how they depend on the
molecular geometry of the catalyst. eoretical
electrocatalytic studies allow exchanging ligands or varying the
chemical environment in a controlled manner.
Computer simulations can therefore not only lead to a
clearer picture of the functioning of a catalyst at the
atomic scale, but they can also lead to suggestions on how
to improve efficiencies.
Developing an affordable and reliable energy
infrastructure for the future is a formidable task. In spite of the
abundant availability of sustainable energy in the form of
sunlight, a large-scale switch to solar energy is still
hindered by high costs of current technologies and the
difficulty to store intermittent electrical energy. Progress
SuSTainab le energY fe aTu r eS
f ig. 2: Snapshots from a molecular dynamics simulation of the desorption of a dye molecule
from a Tio2 semiconductor surface. Panel (a): initially the dye molecule is attached to the surface.
The dye is deprotonated, and the proton (white ball) is attached to a surface oxygen atom (red ball).
Panel (b): one of the dye's bonds to the surface is weakened, which leads to the transfer of the
surface proton to the molecule and finally to the detachment of the molecule from the surface,
see panel (c). The surrounding electrolyte molecules are not shown for clarity.
in these areas can be made possible by bringing together
expertise from various fields. In particular, theoretical
modelling at the atomic scale is a useful tool for a better
understanding of the elementary processes and can lead
to a guided development of new materials.
About the author:
Ralph Gebauer studied physics in Karlsruhe and Lyon.
He obtained his PhD from the Ecole Normale Supérieure
de Lyon in 1999. Aer two years as a postdoc at
Princeton University, he joined the Abdus Salam International
Centre for eoretical Physics in Trieste in 2002 where
he is working as a research scientist in the Statistical
Physics and Condensed Matter Section. His research interests
lie in atomistic simulations using density-functional
theory as well as in computational spectroscopy.
 Available online under: www.bp.com/sectionbodycopy.do?
 W.R. Duncan and O.V. Prezhdo, Annual Review of Physical
Chemistry 58, 143 (2007).
fi g. 3:
of water is an
for the storage
of energy in form
of chemical fuels.
an ideal catalyst
should be able to
perform each of
these steps at the
same cost of