Ring formation in phosphate systems is expected to influence both the magnitude and orientation of the phosphorus (31
P) nuclear magnetic resonance (NMR) chemical shielding anisotropy (CSA) tensor. Ab initio
calculations of the 31
P CSA tensor in both cyclic and acyclic phosphate clusters were performed as a function of the number of phosphate tetrahedral in the system. The calculation of the 31
P CSA tensors employed the GAUSSIAN 98 implementation of the gauge-including atomic orbital (GIAO) method at the Hartree-Fock (HF) level. It is shown that both the 31
P CSA tensor anisotropy, and the isotropic chemical shielding can be used for the identification of cyclic phosphates. The differences between the 31
P CSA tensor in acyclic and cyclic phosphate systems become less pronounced with increasing number of phosphate groups within the ring. The orientation of the principal components for the 31
P CSA tensor shows some variation due to cyclization, most notably with the smaller, highly strained ring systems.