The isotropic magnetic shieldings and chemical shifts in bullvalene have been determined by Feynman path integral Monte Carlo simulations which have been combined with the gauge-including atomic orbital formalism. This setup renders possible the treatment of the quantum and thermal nuclear degrees of freedom in the calculation of NMR quantities. Ab initio Hartree-Fock Hamiltonians have been employed in the present ensemble averaging of NMR parameters. The vibrational motions cause a nuclear deshielding which depends on the topology of the centre studied. The consideration of these corrections leads to a better agreement between measured and calculated chemical shifts. (c) 2006 Elsevier B.V. All rights reserved.