ON THE REACTION OF FNO2 WITH CH3, TERT-BUTYL, AND C13H21

Theoretical studies are reported for the reaction of FNO2 with the rad icals CH3, tert-butyl, and C13H21, Which are templates for the radical site of a hydrogenated diamond (111) surface. All structures are full y optimized using density functional theory based on the B3LYP functio nal. Calibration calculations are performed for CH3 + FNO2 using the c oupled cluster approach, the internally contracted multireference conf iguration interaction method, and second-order perturbation theory bas ed upon the complete-active-space SCF reference wave function. These c alibration calculations support the B3LYP approach for the calculation of bond energies but show that the B3LYP barrier is too low. Combinin g the calibration calculations with the larger clusters yields our bes t estimate of a barrier of about 10 kcal/mol for the reaction of FNO2 with a radical site on hydrogenated diamond (111).