NMR of 129Xe on CO/Ir(111) and on multilayer Xe/Ir(111)

Koch, Matthias; Gerhard, Peter; Jänsch, H.J.

doi:10.1016/j.susc.2006.01.061

Cited by 1 publication

(1 citation statement)

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“…[7][8][9][10][11][12][13][14][15] Xenon is particularly interesting from the point of view of the applicability of PAA, as the NMR of guest 129/131 Xe atoms is widely used to investigate the structure and dynamics of various host materials such as micro-and mesoporous solids, [16][17][18][19][20][21][22][23][24][25][26] liquids and liquid crystals, [27][28][29][30][31][32][33][34][35][36][37] and solid surfaces. [38][39][40][41] Nevertheless, even the prototypic system of xenon gas still challenges the theoretical understanding of Xe NMR. 42,43 PAA treats an ensemble of xenon atoms as a collection of dimers, Xe 2 , for which a binary parametrization of NMR interactions is applied.…”

Section: Introductionmentioning

confidence: 99%

Pairwise additivity in the nuclear magnetic resonance interactions of atomic xenon

Hanni

Lantto

Vaara

2009

Phys. Chem. Chem. Phys.

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Nuclear magnetic resonance (NMR) of atomic (129/131)Xe is used as a versatile probe of the structure and dynamics of various host materials, due to the sensitivity of the Xe NMR parameters to intermolecular interactions. The principles governing this sensitivity can be investigated using the prototypic system of interacting Xe atoms. In the pairwise additive approximation (PAA), the binary NMR chemical shift, nuclear quadrupole coupling (NQC), and spin-rotation (SR) curves for the xenon dimer are utilized for fast and efficient evaluation of the corresponding NMR tensors in small xenon clusters Xe(n) (n = 2-12). If accurate, the preparametrized PAA enables the analysis of the NMR properties of xenon clusters, condensed xenon phases, and xenon gas without having to resort to electronic structure calculations of instantaneous configurations for n > 2. The binary parameters for Xe(2) at different internuclear distances were obtained at the nonrelativistic Hartree-Fock level of theory. Quantum-chemical (QC) calculations at the corresponding level were used to obtain the NMR parameters of the Xe(n) (n = 2-12) clusters at the equilibrium geometries. Comparison of PAA and QC data indicates that the direct use of the binary property curves of Xe(2) can be expected to be well-suited for the analysis of Xe NMR in the gaseous phase dominated by binary collisions. For use in condensed phases where many-body effects should be considered, effective binary property functions were fitted using the principal components of QC tensors from Xe(n) clusters. Particularly, the chemical shift in Xe(n) is strikingly well-described by the effective PAA. The coordination number Z of the Xe site is found to be the most important factor determining the chemical shift, with the largest shifts being found for high-symmetry sites with the largest Z. This is rationalized in terms of the density of virtual electronic states available for response to magnetic perturbations.

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