Theoretical Investigation of the NO3 Radical Addition to Double Bonds of Limonene

• Main Authors: Lei Jiang, Wei Wang, Yi-Sheng Xu
• Format: Article
• Language: English
• Published: MDPI AG 2009-08-01
• Series: International Journal of Molecular Sciences
• Subjects: limonene; nitrate radical (NO3); ab initio; volatile organic compounds
• Online Access: http://www.mdpi.com/1422-0067/10/9/3743/

The addition reactions of NO3 to limonene have been investigated using ab initio methods. Six different possibilities for NO3 addition to the double bonds, which correspond to the two C–C double bonds (endocyclic or exocyclic) have been considered. The negative activation energies for the addition of NO3 to limonene are calculated and the energies of NO3-limonene radical adducts are found to be 14.55 to 20.17 kcal mol-1 more stable than the separated NO3 and limonene at the CCSD(T)/6-31G(d) + CF level. The results also indicate that the endocyclic addition reaction is more energetically favorable than the exocyclic one.