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March 31, 2005 news releases | receive our news
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Follow the Energy: New Technique Enables Scientists to
Track Molecular Energy Transfer in Photosynthesis 
Contact: Lynn Yarris (510 )486-5375, [EMAIL PROTECTED] 
 
BERKELEY, CA – Scientists have been able to follow the
flow of excitation energy in both time and space in a
molecular complex using a new technique called
two-dimensional electronic spectroscopy. While holding
great promise for a broad range of applications, this
technique has already been used to make a surprise
finding about the process of photosynthesis. The
technique was developed by a team of researchers with
the U.S. Department of Energy’s Lawrence Berkeley
National Laboratory (Berkeley Lab) and the University
of California at Berkeley.

  
   
  
Graham Fleming, Deputy Director of Berkeley Lab, led
the development of new technique, called
two-dimensional electronic spectroscopy, that enables
scientists to map the flow of excitation energy
through space with nanometer spatial resolution and
femtosecond temporal resolution.  
  
“I think this will prove to be a revolutionary method
for studying energy flow in complex systems where
multiple molecules interact strongly,” said Graham
Fleming, Deputy Director of Berkeley Lab, and an
internationally acclaimed leader in spectroscopic
studies of the photosynthetic process. “Using
two-dimensional electronic spectroscopy, we can map
the flow of excitation energy through space with
nanometer spatial resolution and femtosecond temporal
resolution.”

Fleming, also a professor of chemistry with UC
Berkeley, is the principal investigator of this
research, and co-author of a paper which appears in
the March 31, 2005 issue of the journal Nature,
entitled “Two-Dimensional Spectroscopy of Electronic
Couplings in Photosynthesis.” Co-authoring the paper
with Fleming were Tobias Brixner, Jens Stenger, Harsha
Vaswani, Minhaeng Cho and Robert Blankenship.

Two-dimensional electronic spectroscopy involves
sequentially flashing a sample with light from three
laser beams, delivered in pulses only 50 femtoseconds
(50 millionths of a billionth of a second) in length,
while a a fourth beam is used as a local oscillator to
amplify and phase-match the resulting spectroscopic
signals. Fleming likens the technique to that of the
early super-heterodyne radios, in which an incoming
high frequency radio signal was converted by an
oscillator to a lower frequency for more controllable
amplification and better reception. In the case of 2-D
electronic spectroscopy, scientists can track the
transfer of energy between molecules that are coupled
(connected) through their electronic and vibrational
states in any photoactive system, macromolecular
assembly or nanostructure.

“This technique should also be useful in studies aimed
at improving the efficiency of molecular solar cells,”
Fleming said. In the Nature paper, he and his
colleagues describe how they successfully used 2-D
electronic spectroscopy to record the first direct
measurement of electronic couplings in the
Fenna-Matthews-Olson (FMO) photosynthetic
light-harvesting protein, a molecular complex in green
sulphur bacteria that absorbs photons and directs the
excitation energy to a reaction center where it can be
converted to chemical energy.

“FMO is a model system for studying energy transfer in
the photosynthetic process because it is relatively
simple (consisting of only seven pigment molecules)
and its chemistry has been well characterized,”
Fleming said. 

“As in all photosynthetic systems, the conversion of
light into chemical energy is driven by electronic
couplings between molecules and we monitored the
process as a function of time and frequency.”

  
  
  
 Through photosynthesis, green plants are able to
capture energy from sunlight and convert it into
chemical energy. By exploiting quantum mechanical
effects, the plants transfer energy from sunlight and
initiate its conversion into chemical energy with an
efficiency of nearly 100-percent. 
  
Fleming and his colleagues expected to find that the
excitation energy from harvested photons in the
light-capturing pigment molecules was transported to
the FMO reaction center molecules step-by-step down
the energy ladder. Instead, they discovered distinct
energy pathways, based on the spatial arrangements of
the molecules, whereby some of the intermediate steps
in the energy ladder are skipped.

“Excitation energy moved through the FMO complex in a
smaller number of steps but larger energy increments
than was previously supposed,” said Fleming. “What
we’re seeing is that Nature exploits quantum
mechanical effects by de-localizing excitation energy
over two or more molecules in a system.”

Photosynthesis should make any short-list of Nature’s
spectacular accomplishments. Through the
photosynthetic process, green plants and cyanobacteria
are able to transfer energy from sunlight and initiate
its conversion into chemical energy with an efficiency
of nearly 100-percent. If we can learn to emulate
Nature’s technique and create artificial versions of
photosynthesis, then we, too, could effectively tap
into the sun as a clean, efficient, sustainable and
carbon-neutral source of energy for our technology. 

“Nature has designed one of the most exquisitely
effective systems for harvesting light, with the steps
happening too fast for energy to be wasted as heat,”
Fleming said. “Current solar power systems, however,
aren’t following Nature’s model.”

  
   
  
In their latest photosynthesis studies, Berkeley
scientists found two main energy transfer pathways in
which some molecules were by-passed in the process. In
one pathway, where there were seven potential energy
transfer steps, the process was completed in three
steps. In the other, where there were six potential
transfer steps, the process was completed in either
three or two steps.  
  
Emulating natural photosynthesis will require a better
understanding of how energy gets transferred from
light-absorbing pigment molecules to the molecules
that make up the energy-converting reaction centers.
Since the extra energy being transferred from one
molecule to the next changes the way each absorbs and
emits light, the flow of energy can be followed
through optical spectroscopy, resolved on a
femtosecond timescale.

Recently, a 2-D femtosecond spectroscopy technique
using infrared light has been used to directly observe
spatial arrangements of molecular systems that are
vibrationally coupled. Fleming and his colleagues were
able to extend this technique to electronic
excitations which require visible light for their
excitation. In this way, they were able to study the
all-important changes and connectivity in the
electronic states of these coupled molecular systems.
They found two main energy transfer pathways in which
some molecules were by-passed in the process because
of insufficient spatial overlap with potential energy
transfer partners. In one pathway, where there were
seven potential energy transfer steps, the process was
completed in three steps. In the other pathway, where
there were six potential transfer steps, the process
was completed in either three or two steps.

“This gives us a new way to think about the design of
artificial photosynthesis systems,” Fleming said. “It
tells us that we must take into consideration the
combined spatial-energetic arrangement of molecules in
a system. If the molecules in a system are properly
arranged in both space and energy, we can transport
energy from one place to another much more
efficiently.”

The next step will be to apply this technique to the
study of the molecular systems in a photosynthetic
reaction center. 

“It’s not enough to just be able to harvest light
efficiently, you also have to be able to efficiently
convert it to a useful form of energy,” Fleming said.

Berkeley Lab is a U.S. Department of Energy national
laboratory located in Berkeley, California. It
conducts unclassified scientific research and is
managed by the University of California. Visit our
Website at www.lbl.gov.


Additional Information
Graham Fleming can be reached by phone at
(510)643-2735. 
For more information about Graham Fleming’s research,
visit his Website at
http://www.cchem.berkeley.edu/~grfgrp 
 
  

  



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