Theoretical investigation of NMR–NQR tensors of hallucinogenic harmine in monomeric and cluster states

In the present study, density functional theory was employed to analyze the structure and nuclear magnetic resonance (NMR) — nuclear quadrupole resonance (NQR) spectra of hallucinogenic harmine in monomeric, dimeric, trimeric, and tetrameric states in the gas phase. Furthermore, the effects of hydrogen and resonance interactions on the values of NMR and NQR parameters of nitrogen nuclei in the four states mentioned above were investigated. The computations at the B3LYP/6-311[Formula: see text]G** level of theory indicated that NQR — NMR parameters of nitrogen nuclei varied for each of the four states and were strongly affected by chemical environment, molecular cluster size and molecular interactions. Accordingly, by increasing the participation of lone pair electrons in resonance interactions and aromaticity development, the values of NMR chemical shielding around them increased, whereas their NQR parameters ([Formula: see text] and [Formula: see text] decreased. In contrast, it could be observed that resonance interaction was not the only effective factor influencing changes in values and trends of NMR — NQR parameters by passing from monomeric state to other ones. Moreover, the negative charge on nitrogen atoms and the possibility of hydrogen bond formation were other important factors influencing NMR — NQR parameters.