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ABSTRACT: Stability and electronic property calculations are performed systematically based on density functional theory at the B3LYP/6-31G(d) level for Td C28 fullerene and exohedral fluorine and trifluoromethyl derivatives C28F4–n(CF3)n (n = 0,1,2,3,4). All the exohedral derivatives that are on the potential energy surfaces are kinetically stable with large HOMO-LUMO gaps. Further investigations show that binding energies of C28F4–n(CF3)n (n = 0,1,2,3,4) molecules are positive, suggesting they are thermodynamically stable. An analysis of the π-orbital axis vector indicates the high strain in Td C28 cage could be greatly released by fluorine and trifluoromethyl decorations. Mulliken charge analysis reveals that adding different electron groups to the Td C28 cage can cause remarkably different charge populations. In addition, from the ionization potential and electron affinity investigations, the C28F4–n(CF3)n (n = 0,1,2,3,4) molecules manifest weak redox properties. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [ABSTRACT FROM AUTHOR]

The mechanisms for the reaction of C2H5S with NO2 are investigated at the QCISD(T)/6-311++G(d, p)//B3LYP/6-311++G(d, p) level on both single and triple potential energy surfaces. The geometries, vibrational frequencies and zero-point energy (ZPE) corrections of all stationary points involved in the title reaction are calculated at the B3LYP/6-311++G(d, p) level. The results show that the reaction is more predominant on the single potential energy surface, while it is negligible on the triple potential energy surface. Without barrier height in the whole process, the major channel is R → C2H5SONO (IM1 and IM2) → P1 (C2H5SO+NO). With much heat released in the formation of C2H5SNO2 (IM3) and the transition state involved in the subsequent step more stable than reactants, P4 (CH3CHS + t-HONO) is subdominant product energetically. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [ABSTRACT FROM AUTHOR]