title: Clathrate Structure Determination by Combining Crystal Structure Prediction with Computational and Experimental129Xe NMR Spectroscopy.
abstract: An approach is presented for the structure determination of clathrates using NMR spectroscopy of enclathrated xenon to select from a set of predicted crystal structures. Crystal structure prediction methods have been used to generate an ensemble of putative structures of o- and m-fluorophenol, whose previously unknown clathrate structures have been studied by129Xe NMR spectroscopy. The high sensitivity of the129Xe chemical shift tensor to the chemical environment and shape of the crystalline cavity makes it ideal as a probe for porous materials. The experimental powder NMR spectra can be used to directly confirm or reject hypothetical crystal structures generated by computational prediction, whose chemical shift tensors have been simulated using density functional theory. For each fluorophenol isomer one predicted crystal structure was found, whose measured and computed chemical shift tensors agree within experimental and computational error margins and these are thus proposed as the true fluorophenol xenon clathrate structures.
authors.affiliation: NMR Research Unit, Faculty of Science, University of Oulu, 90014, Oulu, Finland.|Faculty of Chemistry, Wrocław University, Joliot Curie 14, 50-383, Wrocław, Poland.
authors.forename: Marcin
authors.initials: M
authors.lastname: Selent
authors.affiliation: Computational Systems Chemistry, School of Chemistry, University of Southampton, Southampton, UK.
authors.forename: Jonas
authors.initials: J
authors.lastname: Nyman
authors.affiliation: NMR Research Unit, Faculty of Science, University of Oulu, 90014, Oulu, Finland.
authors.forename: Juho
authors.initials: J
authors.lastname: Roukala
authors.affiliation: Faculty of Chemistry, Wrocław University, Joliot Curie 14, 50-383, Wrocław, Poland.
authors.forename: Marek
authors.initials: M
authors.lastname: Ilczyszyn
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, 90014, Oulu, Finland.
authors.forename: Raija
authors.initials: R
authors.lastname: Oilunkaniemi
authors.affiliation: Computational Systems Chemistry, School of Chemistry, University of Southampton, Southampton, UK.
authors.forename: Peter J
authors.initials: PJ
authors.lastname: Bygrave
authors.affiliation: Laboratory of Inorganic Chemistry, University of Oulu, 90014, Oulu, Finland.
authors.forename: Risto
authors.initials: R
authors.lastname: Laitinen
authors.affiliation: NMR Research Unit, Faculty of Science, University of Oulu, 90014, Oulu, Finland.
authors.forename: Jukka
authors.identifier: http://orcid.org/0000-0003-2190-1775
authors.initials: J
authors.lastname: Jokisaari
authors.affiliation: Computational Systems Chemistry, School of Chemistry, University of Southampton, Southampton, UK.
authors.forename: Graeme M
authors.identifier: http://orcid.org/0000-0001-8396-2771
authors.initials: GM
authors.lastname: Day
authors.affiliation: NMR Research Unit, Faculty of Science, University of Oulu, 90014, Oulu, Finland.
authors.forename: Perttu
authors.identifier: http://orcid.org/0000-0003-0685-7657
authors.initials: P
authors.lastname: Lantto
keywords: Xe NMR spectroscopy; computational chemistry; crystal structure prediction; density functional theory; first principles modelling