14N and 17O electric field gradient tensors in benzamide clusters: Theoretical evidence for cooperative and electronic delocalization effects in N–H⋯O hydrogen bonding

Abstract

Nuclear quadrupole coupling tensors of 14N and 17O nuclei in benzamide clusters (up to n = 6) were calculated via density functional theory. Results revealed that N–H⋯O hydrogen bonds around the benzamide molecule in crystalline lattice have significant influence on 14N and 17O nuclear quadrupole coupling tensors. n-dependent trend in 14N quadrupole coupling tensors significantly correlates with cooperative effects of R(N–H⋯O) hydrogen bond distance. Natural bonding orbital analysis, NBO, was used to rationalize the quadrupole coupling results in terms of substantial n O → σ N – H ∗ charge transfer in (benzamide) n=1−6 clusters. It was found that intermolecular n O → σ N – H ∗ interactions play a key role in cooperative change of 14N and 17O quadrupole coupling tensors. There is an acceptable linear correlation between 14N or 17O quadrupole coupling tensors with strength of Fock matrix elements (Fij). This suggests that both 14N and 17O quadrupole coupling measurements can provide a useful probe for electron delocalization effects in both gaseous and condensed media.