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Chapter - 3 Diversity in Nanosystems

This chapter discusses diversity in nanosystems, specifically fullerenes and carbon clusters. It describes the discovery of buckminsterfullerene (C60) through laser vaporization of graphite followed by time-of-flight mass spectrometry which showed peaks only for C60 and C70. The chapter outlines processes for synthesizing and purifying fullerenes from graphite rods using toluene extraction and chromatography. It also discusses dendritic growth of methanofullerenes and addition of C2 groups to C60 through high-energy ion collisions, as well as properties of C60 powders and single crystals shown via scanning calorimetry and electrical resistivity measurements.

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0% found this document useful (0 votes)
55 views9 pages

Chapter - 3 Diversity in Nanosystems

This chapter discusses diversity in nanosystems, specifically fullerenes and carbon clusters. It describes the discovery of buckminsterfullerene (C60) through laser vaporization of graphite followed by time-of-flight mass spectrometry which showed peaks only for C60 and C70. The chapter outlines processes for synthesizing and purifying fullerenes from graphite rods using toluene extraction and chromatography. It also discusses dendritic growth of methanofullerenes and addition of C2 groups to C60 through high-energy ion collisions, as well as properties of C60 powders and single crystals shown via scanning calorimetry and electrical resistivity measurements.

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Karthik Vk
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Chapter - 3

DIVERSITY IN NANOSYSTEMS

Figure 1. A schematic representation of the structures of graphite, diamond and fullerenes. While the two
dimensional sheets formed by hexagons are packed one over another in graphite, the diamond structure is
three dimensional. Only two fullerenes are shown. The smaller one is buckminsterfullerene, C60. The
bonds between hexagons are more like double bonds showing the corannulene-type substructure. The
double bonds are localised exocyclic to the pentagons giving [5]radialene character to the pentagons and
cyclohexa-1,3,5-triene character to the hexagons.

Figure 2. The experimental set-up used to discover C60. The graphite disk is evaporated with a Nd:YAG
laser and the evaporated carbon plasma is cooled by a stream of helium coming from a pulsed valve. The
clusters of carbon are produced in the integration cup and are expanded into vacuum. The ions are
detected by time of flight mass spectrometry ( For a historical review of this area see, Hugh AlderseyWilliams, The Most Beautiful Molecule, The Discovery of the Buckyball, John Wiley and Sons, Inc.,
New York, 1995).

Figure 3. The mass spectrum of the carbon clusters under various experimental conditions. Under certain
conditions, only C60 and C70 are seen ( For a historical review of this area see, Hugh Aldersey-Williams,
The Most Beautiful Molecule, The Discovery of the Buckyball, John Wiley and Sons, Inc., New York,
1995).

Figure 4. Schematic illustration of the processes involved in the synthesis and purification of fullerenes.
Graphite rods are evaporated in an arc, under He atmosphere. The soot collected is extracted with toluene
and subjected to chromatography.

Figure 5. Schematic showing the synthesis of dendritic methanofullerene, using the established dentritic
growth procedures ( K. L. Wooley, C. J. Hawker, J. M. J. Frechet, F. Wudl, G. Sardanov, S. Shi, C. Li
and M. Rao, J. Am. Chem. Soc. 115 (1993) 9836).

Figure 6. (Bottom) Mass spectrum of a laser evaporated C60 film showing coalescence of fullerenes.
Mass peaks are seen at (C60)n ( C.Yeretzian, K. Hansen, F. Diedrich and R. L. Whetten, Nature 359
(1992) 44). (Top) Collision of high energy ions on C60 results in the addition of C2s to C60. The mass
spectrum here shows the addition of a number of such species ( T. Pradeep and R. G. Cooks, Int. J. Mass
Spectrom. Ion Process 135 (1994) 243). Combined figure originally published in, T. Pradeep, Current
Science, 72 (1997) 124.

Figure 7. Results of a different scanning calorimetric measurement of a powder sample of C60. The arrow
indicates that the data were taken upon warming ( P. A. Heiney, J. E. Fischer, A. R. McGhie, W. J.
Romanow, A. M. Denenstein, J. P. McCauley Jr. and A. B. Smith III, Phys. Rev. Lett. 66 (1991) 2911 ).

Figure 8. Normalised DC electrical resistivity (T) of a K3C60 single crystal. The Tc observed is 19.8K.
0 is the resistivity at T=280 K ( X. D. Xiang, J. G. Hou, G. Briceno, W. A. Vareka, R. Mostovoy, A.
Zettl, V. H. Crespi and M. L. Cohen, Science 256 (1992) 1190).

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