Hartman G D, Schlegel H B
Chem Biol Interact. 1981 Sep;36(3):319-30. doi: 10.1016/0009-2797(81)90075-2.
Utilizing intermediate neglect of differential overlap (INDO) and ab initio methodology, trends in the energy differences between the singlet and triplet states for mono- and polycyclic aryl nitrenium ions have been estimated. Calculations reveal an empirical correlation between the energy separation of the singlet and triplet states of the nitrenium ion and the ability of the parent amine to behave as a carcinogen or mutagen. Non-carcinogenic/non-mutagenic arylamines were characterized by nitrenium ions whose singlet states were much less stable than the triplet. Carcinogenic/mutagenic amines were characterized by nitrenium ions whose singlet states were of similar or greater stability than the triplet. By examination of the charge density at key ring atoms of the singlet and triplet species, a rational approach to the stabilization of one species relative to the other has merged and forms the basis for prediction of genotoxicity in closely related structures. The application of this empirical correlation to the prediction of the carcinogenic/ mutagenic potential of arylamines is discussed.
利用间略微分重叠（INDO）和从头算方法，估算了单环和多环芳基氮鎓离子单重态和三重态之间的能量差趋势。计算结果揭示了氮鎓离子单重态和三重态的能量间隔与母体胺作为致癌物或诱变剂的能力之间的经验相关性。非致癌/非诱变芳胺的特征是其单重态氮鎓离子比三重态稳定性低得多。致癌/诱变胺的特征是其单重态氮鎓离子与三重态具有相似或更高的稳定性。通过检查单重态和三重态物种关键环原子处的电荷密度，形成了一种使一种物种相对于另一种物种稳定的合理方法，并为预测密切相关结构中的遗传毒性奠定了基础。讨论了这种经验相关性在预测芳胺致癌/诱变潜力方面的应用。
