THEORY OF ELECTRONIC-STRUCTURE AND NUCLEAR-QUADRUPOLE INTERACTIONS INHEROIN

A first principle investigation has been carried out for the electric field gradient tensor at the N-14 nucleus in heroin (C21H23NO5) using the Harbee-Fock-Roothaan procedure for determination of the electronic structure employing atomic coordinates based on available X-ray diffr action data. The hydrogen positions were not available from experiment and were determined by energy optimization in our investigations. Our calculated quadrupole coupling constant e(2)qQ for N-14 was found to be -4.906 MHz, the magnitude being in good agreement with the correspo nding recently available magnitude of 5.3163 MHz from nuclear quadrupo le resonance measurements. The value of the asymmetry parameter eta wa s found to be 0.054, the smallness of its size being in agreement with that of the experimental value of 0.028. Possible sources that could further improve the quantitative agreement between theory and experime nt are discussed. The quadrupole interaction parameters for the O-17 a nd H-2 nuclei are presented with the hope that experimental values for them will become available in the future, which would allow a compreh ensive comparison between theory and experiment for all the nuclei in heroin, enabling a thorough test of the calculated electron distributi on in the molecule.