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Abstract
Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Here we determine the location of an H2O molecule isolated within an adsorbed buckminsterfullerene cage, and compare this to the intrafullerene position of HF. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both H2O and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene. The atomistic and electronic structure simulations also reveal significant internal rotational motion consistent with the NIXSW data. Despite this substantial intra-cage interaction, we find that neither HF or H2O contribute to the endofullerene frontier orbitals, confirming the chemical isolation of the encapsulated molecules. We also show that our experimental NIXSW measurements and theoretical data are best described by a mixed adsorption site model.
Highlights
Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage
Through single-molecule scanning tunnelling microscopy, non-contact atomic force microscopy, and valence band photoemission, we show that the frontier orbital structure of the C60 molecule is unaffected by the presence of water inside the cage
Detailed low-energy electron diffraction (LEED) studies by a number of groups have provided compelling evidence that fullerene-induced vacancy reconstruction is prevalent on Cu(111) and Ag(111) surfaces[30,31,32], with scanning tunnelling microscopy (STM) reports
Summary
Molecular surgery provides the opportunity to study relatively large molecules encapsulated within a fullerene cage. Using normal incidence X-ray standing wave (NIXSW) analysis, coupled with density functional theory and molecular dynamics simulations, we show that both H2O and HF are located at an off-centre position within the fullerene cage, caused by substantial intra-cage electrostatic fields generated by surface adsorption of the fullerene. The atomistic and electronic structure simulations reveal significant internal rotational motion consistent with the NIXSW data Despite this substantial intra-cage interaction, we find that neither HF or H2O contribute to the endofullerene frontier orbitals, confirming the chemical isolation of the encapsulated molecules. The measured heights of the H2O and HF molecules above the Ag(111) surface are in good agreement with dispersion-corrected density functional theory (DFT) and molecular dynamics (MD) calculations, confirming the lack of chemical interaction of the encapsulated molecules with the surrounding carbon cage, yet revealing the strong influence of an adsorption-induced intra-fullerene electric field
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