The Royal Swedish Academy of Sciences
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The Royal Swedish Academy of Sciences has decided to award
the 1996 Nobel Prize in Chemistry jointly to
Professor Robert F. Curl, Jr., Rice University, Houston, USA,
for their discovery of fullerenes.
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The discovery of carbon atoms bound in the form of a ball is rewarded
New forms of the element carbon - called fullerenes - in which the atoms are arranged in closed shells was discovered in 1985 by Robert F. Curl, Harold W. Kroto and Richard E. Smalley. The number of carbon atoms in the shell can vary, and for this reason numerous new carbon structures have become known. Formerly, six crystalline forms of the element carbon were known, namely two kinds of graphite, two kinds of diamond, chaoit and carbon(VI). The latter two were discovered in 1968 and 1972.
Fullerenes are formed when vaporised carbon condenses in an atmosphere of inert gas. The gaseous carbon is obtained e.g. by directing an intense pulse of laser light at a carbon surface. The released carbon atoms are mixed with a stream of helium gas and combine to form clusters of some few up to hundreds of atoms. The gas is then led into a vacuum chamber where it expands and is cooled to some degrees above absolute zero. The carbon clusters can then be analysed with mass spectrometry.
Curl, Kroto and Smalley performed this experiment together with graduate students J.R. Heath and S.C. O’Brien during a period of eleven days in 1985. By fine-tuning the experiment they were able in particular to produce clusters with 60 carbon atoms and clusters with 70. Clusters of 60 carbon atoms, C60, were the most abundant. They found high stability in C60, which suggested a molecular structure of great symmetry. It was suggested that C60 could be a "truncated icosahedron cage", a polyhedron with 20 hexagonal (6-angled) surfaces and 12 pentagonal (5-angled) surfaces. The pattern of a European football has exactly this structure, as does the geodetic dome designed by the American architect R. Buckminster Fuller for the 1967 Montreal World Exhibition. The researchers named the newly-discovered structure buckminsterfullerene after him.
The discovery of the unique structure of the C60 was published in the journal Nature and had a mixed reception - both criticism and enthusiastic acceptance. No physicist or chemist had expected that carbon would be found in such a symmetrical form other than those already known. Continuing their work during 1985-90, Curl, Kroto and Smalley obtained further evidence that the proposed structure ought to be correct. Among other things they succeeded in identifying carbon clusters that enclosed one or more metal atoms. In 1990 physicists W. Krätschmer and D.R. Huffman for the first time produced isolable quantities of C60 by causing an arc between two graphite rods to burn in a helium atmosphere and extracting the carbon condensate so formed using an organic solvent. They obtained a mixture of C60 and C70, the structures of which could be determined. This confirmed the correctness of the C60 hypothesis. The way was thus open for studying the chemical properties of C60 and other carbon clusters such as C70, C76, C78 and C84. New substances were produced from these compounds, with new and unexpected properties. An entirely new branch of chemistry developed, with consequences in such diverse areas as astrochemistry, superconductivity and materials chemistry/physics.
He got in touch with Richard E. Smalley, whose research was in cluster chemistry, an important part of chemical physics. A cluster is an aggregate of atoms or molecules, something in between microscopic particles and macroscopic particles. Smalley had designed and built a special laser-supersonic cluster beam apparatus able to vaporise almost any known material into a plasma of atoms and study the design and distribution of the clusters. His paramount interest was clusters of metal atoms, e.g. metals included in semiconductors, and he often performed these investigations together with Robert F. Curl, whose background was in microwave and infra-red spectroscopy.
Atoms form clusters
Carbon atoms per cluster
To gain further clarity Curl, Kroto and Smalley continued their investigations of C60. They attempted to make it react with other compounds. Gases such as hydrogen, nitrous oxide, carbon monoxide, sulphur dioxide, oxygen or ammonia were injected into the gas stream, but no effect on the C60 peak recorded in the mass spectrometer could be demonstrated. This showed that C60 was a slow-reacting compound. It also turned out that all carbon clusters with an even number of carbon atoms from 40-80 (the interval that could be studied) reacted equally slowly. Analogously with C60 all these should then correspond to entirely closed structures, resembling cages. This was in agreement with Euler's law, a mathematical proposition which states that for any polygon with n edges, where n is an even number greater than 22, at least one polyhedron can be constructed with 12 pentagons and (n-20)/2 hexagons, which, in simple terms, states that it is possible with 12 pentagons and with none or more than one hexagon to construct a polyhedron. For large n many different closed structures can occur, thus also for C60, and it was presumably the beautiful symmetry of the proposed structure that gave it the preference.
The combination of chemical inertia in clusters with even numbers of carbon atoms and the possibility that all these could possess closed structures in accordance with Euler's law, led to the proposal that all these carbon clusters should have closed structures. They were given the name fullerenes and conceivably an almost infinite number of fullerenes could exist. The element carbon had thus assumed an almost infinite number of different structures.
C60 and metals
The possibility of producing clusters with a metal atom enclosed gave rise to what was termed the "shrink-wrapping" experiment. Ions of one and the same size or at least similar sizes were gathered in a magnetic trap and subjected to a laser pulse. It then turned out that the laser beam caused the carbon cage to shrink by 2 carbon atoms at a time: at a certain cage size, when the pressure on the metal atom inside became too great, the fragmentation ceased. The shell had then shrunk so that it fitted exactly around the metal atom. For C60Cs+ this size was at C48Cs+, for C60K+ it was at C44K+ and for C60+ at C32+.
Further strong evidence gave rise to new chemistry
Robert F. Curl Jr., was born in 1933 in Alice, Texas, USA: Ph.D. in chemistry in 1957 at University of California, Berkeley, USA. Curl has since 1958 worked at Rice University, where he has been a professor since 1967.
Professor Robert F. Curl Jr.
Sir Harold W. Kroto was born in 1939 in Wisbech, Cambridgeshire, UK. He obtained his Ph.D. in 1964 at the University of Sheffield, UK. In 1967 he moved to the University of Sussex, where he still works. In 1985 he became Professor of Chemistry there and in 1991 Royal Society Research Professor.
Professor Sir Harold W. Kroto
Richard E. Smalley was born in 1943 in Akron, Ohio, USA. Ph.D. in chemistry 1973 at Princeton University, USA. Professor of Chemistry at Rice University since 1981 and also Professor of Physics at the same university since 1990. Member of the National Academy of Sciences in the USA and other bodies.
Professor Richard E. Smalley
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