Adsorption of hydrogen on neutral and charged fullerene: Experiment and theory
- Institut fuer Ionenphysik und Angewandte Physik, University of Innsbruck, Technikerstrasse 25, A-6020 Innsbruck (Austria)
Helium droplets are doped with fullerenes (either C{sub 60} or C{sub 70}) and hydrogen (H{sub 2} or D{sub 2}) and investigated by high-resolution mass spectrometry. In addition to pure helium and hydrogen cluster ions, hydrogen-fullerene complexes are observed upon electron ionization. The composition of the main ion series is (H{sub 2}){sub n}HC{sub m}{sup +} where m= 60 or 70. Another series of even-numbered ions, (H{sub 2}){sub n}C{sub m}{sup +}, is slightly weaker in stark contrast to pure hydrogen cluster ions for which the even-numbered series (H{sub 2}){sub n}{sup +} is barely detectable. The ion series (H{sub 2}){sub n}HC{sub m}{sup +} and (H{sub 2}){sub n}C{sub m}{sup +} exhibit abrupt drops in ion abundance at n= 32 for C{sub 60} and 37 for C{sub 70}, indicating formation of an energetically favorable commensurate phase, with each face of the fullerene ion being covered by one adsorbate molecule. However, the first solvation layer is not complete until a total of 49 H{sub 2} are adsorbed on C{sub 60}{sup +}; the corresponding value for C{sub 70}{sup +} is 51. Surprisingly, these values do not exhibit a hydrogen-deuterium isotope effect even though the isotope effect for H{sub 2}/D{sub 2} adsorbates on graphite exceeds 6%. We also observe doubly charged fullerene-deuterium clusters; they, too, exhibit abrupt drops in ion abundance at n= 32 and 37 for C{sub 60} and C{sub 70}, respectively. The findings imply that the charge is localized on the fullerene, stabilizing the system against charge separation. Density functional calculations for C{sub 60}-hydrogen complexes with up to five hydrogen atoms provide insight into the experimental findings and the structure of the ions. The binding energy of physisorbed H{sub 2} is 57 meV for H{sub 2}C{sub 60}{sup +} and (H{sub 2}){sub 2}C{sub 60}{sup +}, and slightly above 70 meV for H{sub 2}HC{sub 60}{sup +} and (H{sub 2}){sub 2}HC{sub 60}{sup +}. The lone hydrogen in the odd-numbered complexes is covalently bound atop a carbon atom but a large barrier of 1.69 eV impedes chemisorption of the H{sub 2} molecules. Calculations for neutral and doubly charged complexes are presented as well.
- OSTI ID:
- 22105385
- Journal Information:
- Journal of Chemical Physics, Vol. 138, Issue 7; Other Information: (c) 2013 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
36 MATERIALS SCIENCE
ADSORPTION
BINDING ENERGY
CHEMISORPTION
DENSITY FUNCTIONAL METHOD
DEUTERIUM
DOPED MATERIALS
DROPLETS
FULLERENES
GRAPHITE
HELIUM
HYDROGEN
HYDROGEN COMPLEXES
ION PAIRS
ISOTOPE EFFECTS
MASS SPECTROSCOPY