摘要
The cycloaddition reactions of NH to different bonds on C70 have been studied by the first-principles calculations.The results indicate that the reactivity of cycloaddition reactions is determined by the directional curvature,KD,and the larger binding energy of Eb on the bond C5-C？5 can be ascribed to the unique bond which can be treated as the shortest bond of（5.5）-SWCNT in the four [6,6] ring fusion bonds.This work also discloses that the energy gap of different spin states is decided by the electronic density,and that of the frontier obitals for the bond C5-C？5 is larger than the value for the C4-C？4 bond.Furthermore,the transition state investigation of the two bond addition reactions provides a reaction barrier of 11.10 kcal/mol for the NH cycloaddition to the C5-C？5 bond;whereas,the addition reaction on C4-C？4 is a spontaneous pathway.Herein,the dynamics effect illustrates the [2＋1] cycloaddition reaction on the equatorial C5-C？5 bond to be unfavorable.
The cycloaddition reactions of NH to different bonds on C70 have been studied by the first-principles calculations.The results indicate that the reactivity of cycloaddition reactions is determined by the directional curvature,KD,and the larger binding energy of Eb on the bond C5-C？5 can be ascribed to the unique bond which can be treated as the shortest bond of（5.5）-SWCNT in the four [6,6] ring fusion bonds.This work also discloses that the energy gap of different spin states is decided by the electronic density,and that of the frontier obitals for the bond C5-C？5 is larger than the value for the C4-C？4 bond.Furthermore,the transition state investigation of the two bond addition reactions provides a reaction barrier of 11.10 kcal/mol for the NH cycloaddition to the C5-C？5 bond;whereas,the addition reaction on C4-C？4 is a spontaneous pathway.Herein,the dynamics effect illustrates the [2＋1] cycloaddition reaction on the equatorial C5-C？5 bond to be unfavorable.
基金
supported by the National Natural Science Foundation of China (No.21073034)
the State Key Laboratory of Structural Chemistry (No.20090060)
