Heating a bowl of single-molecule-soup: structure and desorption energetics of water-encapsulated open-cage [60] fullerenoid anions in the gas-phase.
Phys Chem Chem Phys
; 13(20): 9818-23, 2011 May 28.
Article
em En
| MEDLINE
| ID: mdl-21503296
ABSTRACT
The gas-phase unimolecular decay kinetics of an anionic, open-cage [60] fullerene derivative encapsulating one water molecule is studied by means of black-body IR radiation induced dissociation (BIRD) in the temperature programmable ion trap of a Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometer. The primary reaction channel observed is escape of the water molecule from the fullerenoid bowl. The rate constants for this water loss as a function of temperature are evaluated using the Arrhenius equation to yield an activation energy of 104 ± 4 kJ mol(-1). A complementary ion mobility spectrometry study contrasting the water-encapsulated and the empty fullerene cages finds identical collision cross sections to within experimental error-supporting the structural assignment of this gas-phase anion as an endohedral (i.e. encapsulated) species. Both experiments were compared with quantum-chemical computations which well-describe the transition state for water desorption and the concomitant binding and activation energies.
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01-internacional
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MEDLINE
Idioma:
En
Revista:
Phys Chem Chem Phys
Ano de publicação:
2011
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Article