Chemical shielding of H2O and HF encapsulated inside a C60 cage

DOI: 10.1038/s42004-021-00569-0

Authors: Samuel P. Jarvis (Lancaster University) , Hongqian Sang (Jianghan University; King’s College London) , Filipe Junqueira (The University of Nottingham) , Oliver Gordon (The University of Nottingham) , Joe E. A. Hodgkinson (The University of Nottingham) , Alex Saywell (The University of Nottingham) , Philipp Rahe (Universität Osnabrück) , Salvatore Mamone (The University of Nottingham) , Simon Taylor (The University of Nottingham) , Adam Sweetman (University of Leeds) , Jeremy Leaf (The University of Nottingham) , David A. Duncan (Diamond Light Source) , Tien-Lin Lee (Diamond Light Source) , Pardeep K. Thakur (Diamond Light Source) , Gabriella Hoffman (The University of Southampton) , Richard J. Whitby (The University of Southampton) , Malcolm H. Levitt (The University of Southampton) , Georg Held (Diamond Light Source) , Lev Kantorovich (King’s College London) , Philip Moriarty (The University of Nottingham) , Robert G. Jones (The University of Nottingham)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Communications Chemistry , VOL 4

State: Published (Approved)
Published: September 2021
Diamond Proposal Number(s): 12979 , 15022

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.

Subject Areas: Materials, Physics, Chemistry


Instruments: I09-Surface and Interface Structural Analysis

Added On: 24/09/2021 10:55

Documents:
s42004-021-00569-0.pdf

Discipline Tags:

Physical Chemistry Chemistry Materials Science

Technical Tags:

Diffraction Spectroscopy X-ray Standing Wave (XSW) X-ray Photoelectron Spectroscopy (XPS)