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129 Xe NMR chemical shift in Xe@C 60 calculated at experimental conditions: Essential role of the relativity, dynamics, and explicit solvent
Author(s) -
Standara Stanislav,
Kulhánek Petr,
Marek Radek,
Straka Michal
Publication year - 2013
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23334
Subject(s) - chemistry , xenon , molecular dynamics , chemical shift , atomic physics , computational chemistry , physics
The isotropic 129 Xe nuclear magnetic resonance (NMR) chemical shift (CS) in Xe@C 60 dissolved in liquid benzene was calculated by piecewise approximation to faithfully simulate the experimental conditions and to evaluate the role of different physical factors influencing the 129 Xe NMR CS. The 129 Xe shielding constant was obtained by averaging the 129 Xe nuclear magnetic shieldings calculated for snapshots obtained from the molecular dynamics trajectory of the Xe@C 60 system embedded in a periodic box of benzene molecules. Relativistic corrections were added at the Breit–Pauli perturbation theory (BPPT) level, included the solvent, and were dynamically averaged. It is demonstrated that the contribution of internal dynamics of the Xe@C 60 system represents about 8% of the total nonrelativistic NMR CS, whereas the effects of dynamical solvent add another 8%. The dynamically averaged relativistic effects contribute by 9% to the total calculated 129 Xe NMR CS. The final theoretical value of 172.7 ppm corresponds well to the experimental 129 Xe CS of 179.2 ppm and lies within the estimated errors of the model. The presented computational protocol serves as a prototype for calculations of 129 Xe NMR parameters in different Xe atom guest–host systems. © 2013 Wiley Periodicals, Inc.