Chemists find new dimension to rules for reactions

ScienceDaily (Oct. 20, 2011) — Theoretical chemists at Emory University have solved an important mystery about the rates of chemical reactions and the so-called Polanyi rules.

The findings, published in the journal Science, reveal why a reaction involving methane does not conform to the known rules, a problem that has baffled physical chemists in recent years.

"We showed that a pre-reactive, long-range force can align the reaction of a chorine atom with methane, or natural gas, in a way that actually inhibits the reaction," says Joel Bowman, a professor of theoretical chemistry at Emory and the Cherry L. Emerson Center for Computational Chemistry. "We believe that the theoretical work that we did has extended and modified the Polanyi rules."

Bowman published the results with Gabor Czako, a post-doctoral fellow in theoretical chemistry who performed most of the complex computational and mathematical analyses that uncovered the results.

Long-range, their findings could play a role in the development of cleaner, more efficient fuels.

Understanding the dynamics of chemical reactions is key to driving reactions efficiently, whether in a laboratory experiment or in an industrial application. In 1986, John Polanyi shared the Nobel Prize in chemistry, in part by providing general rules for how different forms of energy affect the rates of reactions.

"The Polanyi rules tell you the best way to deposit energy in a simple molecule to make a chemical reaction occur," Bowman says. "It's a bit like knowing in advance how to invest $1,000 to maximize the return on investment."

Polanyi developed the framework based on studies of simple reactions of chlorine and fluorine atoms with hydrogen gas. As technology has advanced in recent years, some chemists began testing the Polanyi rules for more complicated reactions, and the rules appeared to break down. Most notably, sophisticated molecular beam experiments by Kopin Liu at the Institute of Atomic and Molecular Sciences in Taiwan showed that the reaction of halogen atoms with methane did not conform to the rules.

"Suddenly, the rules appeared to have changed, and no one could explain why," Bowman says. "We decided to roll up our sleeves and attack the problem theoretically."

Bowman and Czako drew from the computational power of the Emerson Center, specialized software and analytical techniques. They first created theoretical-computational simulations of the experiments done by Liu and others, and then described the results mathematically.

"Our calculations showed essentially an exact agreement with the experimental results," Bowman says. "When theory and experiment agree you're happy, but you still want to know why."

Determining why the reactions did not conform to the Polanyi rules was another complicated task, involving quantum mechanics and forces that govern the reaction down to the atomic level.

"As theoreticians, we're able to zoom in and look at the results of our calculations in a way that's virtually impossible in an experiment," Bowman says.

They identified a subtle interplay between the Polanyi rules and a pre-reactive long-range force of methane with chlorine. If you follow the Polanyi rules, this long-range force, or steric control, will misalign the reactants, preventing them from docking correctly and inhibiting a reaction. But if you apportion the energy in the opposite way to the rules, the misalignment is wiped out and the reaction occurs.

"This long-range force was playing a bigger role than was previously realized," Bowman says. "It can actually trump the Polanyi rules, at least in the reactions that Liu and we looked at. The Polanyi rules are certainly not all wrong, they just appear to be too simple to apply to more complex reactions."

The research was funded by the National Science Foundation and the U.S. Department of Energy.

The reactive properties of natural gas are of particular interest since it is an important fuel. Bowman and Czako are now applying their techniques to study the combustion of methane and oxygen, which produces carbon dioxide. "It's important to understand the dynamics of this reaction, because it might lead to more efficient ways to produce fuel, and a reduction in the levels of pollution emitted," Bowman says.

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The above story is reprinted from materials provided by Emory University. The original article was written by Carol Clark.

Note: Materials may be edited for content and length. For further information, please contact the source cited above.

Journal Reference:

G. Czako, J. M. Bowman. Dynamics of the Reaction of Methane with Chlorine Atom on an Accurate Potential Energy Surface. Science, 2011; 334 (6054): 343 DOI: 10.1126/science.1208514

Note: If no author is given, the source is cited instead.

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Watching motion of electrons in molecules during chemical reactions

ScienceDaily (Oct. 14, 2011) — A research group led by ETH Zurich has now, for the first time, visualized the motion of electrons during a chemical reaction. The new findings in the experiment are of fundamental importance for photochemistry and could also assist the design of more efficient solar cells.

In 1999, Ahmed Zewail was awarded the nobel prize in chemistry for his studies of chemical reactions using ultrashort laser pulses. Zewail was able to watch the motion of atoms and thus visualize transition states on the molecular level. Watching the dynamics of single electrons was still considered a dream at that time. Thanks to the latest developments in laser technology and intense research in the field of attosecond spectroscopy (1 attosecond = 10-18 s) the research has developed fast. For the first time, Prof. Hans Jakob Wörner from the Laboratory of Physical Chemistry at ETH Zurich, together with colleagues from Canada and France, was able to record electronic motion during a complete chemical reaction. The experiment is described in the latest issue of Science.

The research team irradiated nitrogen dioxide molecules (NO2) with a very short ultraviolet pulse. Subsequently, the molecule takes up the energy from the pulse which sets the electrons in motion. The electrons start rearranging themselves, which causes the electron cloud to oscillate between two different shapes for a very short time, before the molecule starts to vibrate and eventually decomposes into nitric oxide and an oxygen atom.

Conical intersections

Nitrogen dioxide has model character with respect to understanding electronic motion. In the NO2 molecule, two states of the electrons can have the same energy for a particular geometry -- commonly described as conical intersection. The conical intersection is very important for photochemistry and frequently occurs in natural chemical processes induced by light. The conical intersection works like a dip-switch. For example, if the retina of a human eye is irradiated by light, the electrons start moving, and the molecules of the retina (retinal) change their shape, which finally converts the information of light to electrical information for the human brain. The special aspect about conical intersections is that the motion of electrons is transferred to a motion of the atoms very efficiently.

Snapshot of an electron

In an earlier article, Hans Jakob Wörner has already published how attosecond spectroscopy can be used for watching the motion of electrons. The first weak ultraviolet pulse sets the electrons in motion. The second strong infrared pulse then removes an electron from the molecule, accelerates it and drives it back to the molecule. As a result, an attosecond light pulse is emitted, which carries a snapshot of the electron distribution in the molecule. Wörner illustrates the principle of attosecond spectroscopy: "The experiment can be compared to photographs, which, for example, image a bullet shot through an apple. The bullet would be too fast for the shutter of a camera, resulting in a blurred image. Therefore, the shutter is left open and the picture is illuminated with light flashes, which are faster than the bullet. That's how we get our snap-shot."

From the experiment to solar cells

When the electron returns to the molecule, it releases energy in the form of light. In the experiment, Wörner and his colleagues measured the light of the electrons and were therefore able to deduce detailed information on the electron distribution and its evolution with time. This information reveals details of chemical reaction mechanisms that were not accessible to most of previous experimental techniques. The experiment on NO2 helps understanding fundamental processes in molecules and is an ideal extension of computer simulations of photochemical processes: "What makes our experiment so important is that it verifies theoretical models," says Wörner. The immense interest in photochemical processes is not surprising, as this area of research aims at improving solar cells and making artificial photosynthesis possible.

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The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by ETH Zürich.

Journal Reference:

H. J. Worner, J. B. Bertrand, B. Fabre, J. Higuet, H. Ruf, A. Dubrouil, S. Patchkovskii, M. Spanner, Y. Mairesse, V. Blanchet, E. Mevel, E. Constant, P. B. Corkum, D. M. Villeneuve. Conical Intersection Dynamics in NO2 Probed by Homodyne High-Harmonic Spectroscopy. Science, 2011; 334 (6053): 208 DOI: 10.1126/science.1208664

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here

Watching motion of electrons in molecules during chemical reactions

ScienceDaily (Oct. 14, 2011) — A research group led by ETH Zurich has now, for the first time, visualized the motion of electrons during a chemical reaction. The new findings in the experiment are of fundamental importance for photochemistry and could also assist the design of more efficient solar cells.

In 1999, Ahmed Zewail was awarded the nobel prize in chemistry for his studies of chemical reactions using ultrashort laser pulses. Zewail was able to watch the motion of atoms and thus visualize transition states on the molecular level. Watching the dynamics of single electrons was still considered a dream at that time. Thanks to the latest developments in laser technology and intense research in the field of attosecond spectroscopy (1 attosecond = 10-18 s) the research has developed fast. For the first time, Prof. Hans Jakob Wörner from the Laboratory of Physical Chemistry at ETH Zurich, together with colleagues from Canada and France, was able to record electronic motion during a complete chemical reaction. The experiment is described in the latest issue of Science.

The research team irradiated nitrogen dioxide molecules (NO2) with a very short ultraviolet pulse. Subsequently, the molecule takes up the energy from the pulse which sets the electrons in motion. The electrons start rearranging themselves, which causes the electron cloud to oscillate between two different shapes for a very short time, before the molecule starts to vibrate and eventually decomposes into nitric oxide and an oxygen atom.

Conical intersections

Nitrogen dioxide has model character with respect to understanding electronic motion. In the NO2 molecule, two states of the electrons can have the same energy for a particular geometry -- commonly described as conical intersection. The conical intersection is very important for photochemistry and frequently occurs in natural chemical processes induced by light. The conical intersection works like a dip-switch. For example, if the retina of a human eye is irradiated by light, the electrons start moving, and the molecules of the retina (retinal) change their shape, which finally converts the information of light to electrical information for the human brain. The special aspect about conical intersections is that the motion of electrons is transferred to a motion of the atoms very efficiently.

Snapshot of an electron

In an earlier article, Hans Jakob Wörner has already published how attosecond spectroscopy can be used for watching the motion of electrons. The first weak ultraviolet pulse sets the electrons in motion. The second strong infrared pulse then removes an electron from the molecule, accelerates it and drives it back to the molecule. As a result, an attosecond light pulse is emitted, which carries a snapshot of the electron distribution in the molecule. Wörner illustrates the principle of attosecond spectroscopy: "The experiment can be compared to photographs, which, for example, image a bullet shot through an apple. The bullet would be too fast for the shutter of a camera, resulting in a blurred image. Therefore, the shutter is left open and the picture is illuminated with light flashes, which are faster than the bullet. That's how we get our snap-shot."

From the experiment to solar cells

When the electron returns to the molecule, it releases energy in the form of light. In the experiment, Wörner and his colleagues measured the light of the electrons and were therefore able to deduce detailed information on the electron distribution and its evolution with time. This information reveals details of chemical reaction mechanisms that were not accessible to most of previous experimental techniques. The experiment on NO2 helps understanding fundamental processes in molecules and is an ideal extension of computer simulations of photochemical processes: "What makes our experiment so important is that it verifies theoretical models," says Wörner. The immense interest in photochemical processes is not surprising, as this area of research aims at improving solar cells and making artificial photosynthesis possible.

Recommend this story on Facebook, Twitter,
and Google +1:

Other bookmarking and sharing tools:

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by ETH Zürich.

Journal Reference:

H. J. Worner, J. B. Bertrand, B. Fabre, J. Higuet, H. Ruf, A. Dubrouil, S. Patchkovskii, M. Spanner, Y. Mairesse, V. Blanchet, E. Mevel, E. Constant, P. B. Corkum, D. M. Villeneuve. Conical Intersection Dynamics in NO2 Probed by Homodyne High-Harmonic Spectroscopy. Science, 2011; 334 (6053): 208 DOI: 10.1126/science.1208664

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here

New driving force for chemical reactions

ScienceDaily (June 9, 2011) — New research just published in the journal Science by a team of chemists at the University of Georgia and colleagues in Germany shows for the first time that a mechanism called tunneling control may drive chemical reactions in directions unexpected from traditional theories.

The finding has the potential to change how scientists understand and devise reactions in everything from materials science to biochemistry.

The discovery was a complete surprise and came following the first successful isolation of a long-elusive molecule called methylhydroxycarbene by the research team. While the team was pleased that it had "trapped" the prized compound in solid argon through an extremely low-temperature experiment, they were surprised when it vanished within a few hours. That prompted UGA theoretical chemistry professor Wesley Allen to conduct large scale, state-of-the-art computations to solve the mystery.

"What we found was that the change was being controlled by a process called quantum mechanical tunneling," said Allen, "and we found that tunneling can supersede the traditional chemical reactivity processes of kinetic and thermodynamic control. We weren't expecting this at all."

What had happened? Clearly, a chemical reaction had taken place, but only inert argon atoms surrounded the compound, and essentially no thermal energy was available to create new molecular arrangements. Moreover, said Allen, "the observed product of the reaction, acetaldehyde, is the least likely outcome among conceivable possibilities."

Other authors of the paper include Professor Peter Schreiner and his group members Hans Peter Reisenauer, David Ley and Dennis Gerbig of the Justus-Liebig University in Giessen, Germany. Graduate student Chia-Hua Wu at UGA undertook the theoretical work with Allen.

Quantum tunneling isn't new. It was first recognized as a physical process decades ago in early studies of radioactivity. In classical mechanics, molecular motions can be understood in terms of particles roaming on a potential energy surface. Energy barriers, visualized as mountain passes on the surface, separate one chemical compound from another.

For a chemical reaction to occur, a molecular system must have enough energy to "get over the top of the hill," or it will come back down and fail to react. In quantum mechanics, particles can get to the other side of the barrier by tunneling through it, a process that seemingly requires imaginary velocities. In chemistry, tunneling is generally understood to provide secondary correction factors for the rates of chemical reactions but not to provide the predominant driving force.

(The strange world of quantum mechanics has been subject to considerable interest and controversy over the last century, and Austrian physicist Erwin Schrödinger's thought-experiment called "Schrödinger's Cat" illustrates how perplexing it is to apply the rules and laws of quantum mechanics to everyday life.)

"We knew that the rate of a reaction can be significantly affected by quantum mechanical tunneling," said Allen. "It becomes especially important at low temperatures and for reactions involving light atoms. What we discovered here is that tunneling can dominate a reaction mechanism sufficiently to redirect the outcome away from traditional kinetic control. Tunneling can cause a reaction that does not have the lowest activation barriers to occur exclusively."

Allen suggests a vivid analogy between the behavior of methylhydroxycarbene and Schrödinger's iconic cat.

"The cat cannot jump out of its box of deadly confinement because the walls are too high, so it conjures a Houdini-like escape by bursting through the thinnest wall," he said.

The fact that new ideas about tunneling came from the isolation of methylhydroxycarbene was the kind of serendipity that runs through the history of science. Schreiner and his team had snagged the elusive compound, and that was reason enough to celebrate, Allen said. But the surprising observation that it vanished within a few hours raised new questions that led to even more interesting scientific discoveries.

"The initiative to doggedly follow up on a 'lucky observation' was the key to success," said Allen. "Thus, a combination of persistent experimentation and exacting theoretical analysis on methylhydroxycarbene and its reactivity led to the concept I dubbed tunneling control, which may be characterized as `a type of nonclassical kinetic control wherein the decisive factor is not the lowest activation barrier'."

While the process was unearthed for the specific case of methylhydroxycarbene at extremely low temperatures, Allen said that tunneling control "can be a general phenomenon, especially if hydrogen transfer is involved, and such processes need not be restricted to cryogenic temperatures."

Allen's research was funded by the U.S. Department of Energy.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by University of Georgia.

Journal Reference:

Peter R. Schreiner, Hans Peter Reisenauer, David Ley, Dennis Gerbig, Chia-Hua Wu, Wesley D. Allen. Methylhydroxycarbene: Tunneling Control of a Chemical Reaction. Science, 10 June 2011: Vol. 332 no. 6035 pp. 1300-1303 DOI: 10.1126/science.1203761

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here

New driving force for chemical reactions

ScienceDaily (June 9, 2011) — New research just published in the journal Science by a team of chemists at the University of Georgia and colleagues in Germany shows for the first time that a mechanism called tunneling control may drive chemical reactions in directions unexpected from traditional theories.

The finding has the potential to change how scientists understand and devise reactions in everything from materials science to biochemistry.

The discovery was a complete surprise and came following the first successful isolation of a long-elusive molecule called methylhydroxycarbene by the research team. While the team was pleased that it had "trapped" the prized compound in solid argon through an extremely low-temperature experiment, they were surprised when it vanished within a few hours. That prompted UGA theoretical chemistry professor Wesley Allen to conduct large scale, state-of-the-art computations to solve the mystery.

"What we found was that the change was being controlled by a process called quantum mechanical tunneling," said Allen, "and we found that tunneling can supersede the traditional chemical reactivity processes of kinetic and thermodynamic control. We weren't expecting this at all."

What had happened? Clearly, a chemical reaction had taken place, but only inert argon atoms surrounded the compound, and essentially no thermal energy was available to create new molecular arrangements. Moreover, said Allen, "the observed product of the reaction, acetaldehyde, is the least likely outcome among conceivable possibilities."

Other authors of the paper include Professor Peter Schreiner and his group members Hans Peter Reisenauer, David Ley and Dennis Gerbig of the Justus-Liebig University in Giessen, Germany. Graduate student Chia-Hua Wu at UGA undertook the theoretical work with Allen.

Quantum tunneling isn't new. It was first recognized as a physical process decades ago in early studies of radioactivity. In classical mechanics, molecular motions can be understood in terms of particles roaming on a potential energy surface. Energy barriers, visualized as mountain passes on the surface, separate one chemical compound from another.

For a chemical reaction to occur, a molecular system must have enough energy to "get over the top of the hill," or it will come back down and fail to react. In quantum mechanics, particles can get to the other side of the barrier by tunneling through it, a process that seemingly requires imaginary velocities. In chemistry, tunneling is generally understood to provide secondary correction factors for the rates of chemical reactions but not to provide the predominant driving force.

(The strange world of quantum mechanics has been subject to considerable interest and controversy over the last century, and Austrian physicist Erwin Schrödinger's thought-experiment called "Schrödinger's Cat" illustrates how perplexing it is to apply the rules and laws of quantum mechanics to everyday life.)

"We knew that the rate of a reaction can be significantly affected by quantum mechanical tunneling," said Allen. "It becomes especially important at low temperatures and for reactions involving light atoms. What we discovered here is that tunneling can dominate a reaction mechanism sufficiently to redirect the outcome away from traditional kinetic control. Tunneling can cause a reaction that does not have the lowest activation barriers to occur exclusively."

Allen suggests a vivid analogy between the behavior of methylhydroxycarbene and Schrödinger's iconic cat.

"The cat cannot jump out of its box of deadly confinement because the walls are too high, so it conjures a Houdini-like escape by bursting through the thinnest wall," he said.

The fact that new ideas about tunneling came from the isolation of methylhydroxycarbene was the kind of serendipity that runs through the history of science. Schreiner and his team had snagged the elusive compound, and that was reason enough to celebrate, Allen said. But the surprising observation that it vanished within a few hours raised new questions that led to even more interesting scientific discoveries.

"The initiative to doggedly follow up on a 'lucky observation' was the key to success," said Allen. "Thus, a combination of persistent experimentation and exacting theoretical analysis on methylhydroxycarbene and its reactivity led to the concept I dubbed tunneling control, which may be characterized as `a type of nonclassical kinetic control wherein the decisive factor is not the lowest activation barrier'."

While the process was unearthed for the specific case of methylhydroxycarbene at extremely low temperatures, Allen said that tunneling control "can be a general phenomenon, especially if hydrogen transfer is involved, and such processes need not be restricted to cryogenic temperatures."

Allen's research was funded by the U.S. Department of Energy.

Story Source:

The above story is reprinted (with editorial adaptations by ScienceDaily staff) from materials provided by University of Georgia.

Journal Reference:

Peter R. Schreiner, Hans Peter Reisenauer, David Ley, Dennis Gerbig, Chia-Hua Wu, Wesley D. Allen. Methylhydroxycarbene: Tunneling Control of a Chemical Reaction. Science, 10 June 2011: Vol. 332 no. 6035 pp. 1300-1303 DOI: 10.1126/science.1203761

Note: If no author is given, the source is cited instead.

Disclaimer: Views expressed in this article do not necessarily reflect those of ScienceDaily or its staff.

View the original article here