A theoretical examination of the isomerization of BrONO2 to BrOONO

The structural properties of the BrONO2 ↔ BrOONO isomerization transition states are examined using density functional calculations in conjunction with different basis sets. The energy barriers for the isomerization pathways at the CBS-QB3 level of theory are large enough, from 34.2 up to 32.5 kcal mol−1, to prevent the isomerization of BrONO2 to either cis-perp or trans-perp BrOONO. But, the energy barriers of only 8.3 and 4.7 kcal mol−1 make feasible an interconversion process of cis-perp BrOONO and trans-perp BrOONO, respectively, to BrONO2.