Quantitative Theoretical Study on the Molecular Surface Reactivities and Molecular Aromaticities of 1,1’‐BTO, Its Anion, BTO _anion , and Its Radical, BTO _biradical

ABSTRACT 1,1´‐Dihydroxam‐5,5´‐bisazide (1,1´‐BTO) is the precursor for the well‐known energetic material dihydroxylammonium 5,5´‐bistetrazole‐1,1´‐diolate. It always appears in an anionic state, BTO anion , and a free radical state, BTO biradical , depending on the chemical environments during its reactions. To demonstrate their molecular surface reactivity, starting from their electronic structure optimized on the theory level of ωB97XD/def2‐TZVP, theoretical calculations and results discussions were carried out on their atomic dipole moment corrected Hirshfeld population charges, molecular surface electrostatic potential, molecular surface average local ionization energy; to deeply understand thermodynamic stabilities characterized by their aromaticities, nuclear‐independent chemical shift (NICS) along with the direction perpendicular to their molecular plane, its variant free of in‐plane component NICS, magnetically induced current, were calculated from the wave function obtained on the theory level of PBE0/6‐311++G** and discussed. These discussions and conclusions are expected to enrich the deeper understanding of the states presented by 1,1´‐BTO during the reaction process.