Theoretical investigation on the potential energy surface for the reactions of B, Al and Ga with NO

The structures, binding energies and vibrational frequencies of various MNO structural isomers (M = B, Al and Ga) in their ground tripler states have been determined using the density functional (B3LYP, BP86 and B3PW91) and M P2 methods. The potential energy surfaces of the M+NO reactions have been d eveloped at the B3LYP/6-311+G(d) level of theory, and transition states on the isomerization potential energy surfaces have been characterized. Our ca lculation results show that four BNO isomers, namely, nitrosyl BNO, isonitr osyl BON, side-bonded B-eta(2)-NO and the inserted NBO molecules are statio nary points, while for Al and Ga, only the MNO (nitrosyl), MON (isonitrosyl ) and the OMN (insertion) molecules are local minimum. The B+NO reaction pr oducts are more strongly bonded compared to the Al and Ga+NO systems due to strong covalent bonding. The interactions of B, Al and Ga atoms with NO to generate nitrosyl and isonitrosyl addition molecules are barrierless, but subsequent isomerization reactions to form the side-bonded molecules and th e inserted products require activation energy. (C) 2000 Elsevier Science B. V. All rights reserved.