Theoretical Studies On Electronic Structures And Spectrum For Several Fullerenes As Well As The Corresponding Chlorinated Dericatives

Fullerenes have captured a great deal of attention for the passed years.Especially for the non-IPR isomers with fused pentagons,they have a large number and are more reactive than the IPR fullerenes.In order to explore the potential applications of non-IPR fullerenes,probe their specific physicochemical properties,and identify the isomers,we detect the geometrical/electronic structures and spectral characteristics for the several fullerenes as well as their corresponding chloride by using the density functional theory(DFT)and the time-density functional theory(TD-DFT)method.The main contents of this paper are listed as follows:1.Systematic research of D2_#916 C56 and C2v-#913C56 as well as their corresponding chlorinated species C2-#916C56Cl12 and C2v-#913C56Cl10 has been done at the DFT level.We find that D2-#916C56 is more stable than C2v-#913C56.X-ray photoelectron(XPS)and near-edge X-ray absorption fine structure(NEXAFS)spectrum of C56 isomers show strong isomer dependence,which means that characteristic peaks of spectras can be used to distinguish isomers.We also find that the electronic structure and simulated X-ray spectrum have been changed after chlorination.Meawhile,Ultraviolet-visible(UV-Vis)spectra of two chlorides C2-C56Cl12 and C2v-C56Cl10 have been simulated at TD-DFT level.The calculated UV-Vis spectras are found to be in good agreement with the experimental counterparts.2.Theoretical results of Cs-#4169C66 and C2v-#4348C66 as well as the corresponding chloride Cl-#4169C66Cl6,C1-#4169C66Cl10 and Cs-#4348C66CI10 have been received using DFT method.Cs-#4169C66 is the most stable isomer in all C66 fullerences,and C2v-#4348C66 is the second one.Meanwhile,there is a triple sequentially fused pentagons(TSFP)for Cs-#4169C66 and two Double fused pentagons(DFP)for C2v-#4348C66.XPS and NEXAFS speactrum of C66 also show "fingerprints" which originated from TSFP and DFP mainly.Moreover,results show that chloration can well cut down the reactivity and change the geometrical/electronic structures of non-IPR C66.In addition,UV-Vis spectras of Cl-#4169C66Cl6,C1-#4169C66CI10 and Cs-#4348C66Cl10 have been simulated using TD-DFT,and main adsorption peaks have been assigned to relevant electronic transimitions.The simulated UV-Vis spectras coincide with experimental data.3.Theoretical calculation for IPR fullerene D3h-#24108C78 and non-IPR fullerene C1-#23863C78 as well as the corresponding Cl-#23863C78C18 have been accomplished at DFT level.C1-#23863C78 is more stable than D3h-#24108C78,XPS and NEXAFS speactrum have presented "fingerprints" for both IPR and non-IPR isomers.And the DFP and Pyrene sites carbons make contributes to the particular peaks.The geometrical/electronic structures and spectrum of Cl-#223863C78 have also been changed after chloridizing.We have further simulated the infrared radiation(IR)spectrum for C1-#23863C78Cl8 which agrees the experimental spectrum.