Theoretical Studies On Electronic Structures And X-ray Spectra Of Several Novel Fullerenes

Doped and non-IPR fullerenes which are known as novel fullerenes have received a great of attention.In order to explore the potential applications of novel fullerenes,probe their specific physicochemical properties,and identify the isomers,we detect the stabilities,geometrical/electronic structures and X-ray spectra characteristics of three kinds of novel fullerenes systematically by using density functional theory(DFT).The main contents of this paper are listed as follows:1.DFT calculations are carried out to look for the most and the second stable configurations of 23 isomers of C58B2,which are obtained by substituting two C atoms of Ih-C60 with B atoms.Theoretical research on electronic structures and spectral properties are performed.After the incorporation of B atoms,C58B2 isomers display peculiar geometrical/electronic structures.The singlet state 1,4-C58B2 is the most stable isomers,and the singlet state 1,416-C58B2 is the second stable one.Obvious difference have been observed between the X-ray photoelectron spectroscopy(XPS)of C atoms of the two C58B2 isomers,and the ionization potential(IP)values of the C atoms belonging to CCB type display a red shift about 1 eV compared to that of Ih-C60.In the near-edge X-ray absorption fine structure(NEXAFS)of the two C58B2 isomers,peak A which mainly contributed by C atoms of CCB type can be regarded as the fingerprint peaks.However,the XES of two C58B2 isomers and Ih-C60 exhibit similar features.2.The XPS,NEXAFS,as well as the ground-state electronic/geometrical structures of recently captured Non-IPR#8064C70,the corresponding chlorinated derivative#8064C70Cl10 and the IPR obeying#8149C70 have been calculated at DFT level.Meanwhile,have been simulated Ultraviolet-visible(UV-vis)absorption spectrum of#8064C70Cl10 by the Time dependent density functional theory(TD-DFT)method,and the main adsorption peaks have been assigned to relevant electronic transimitions.Effective changes in the electronic structures and simulated X-ray spectra have been observed between two C70 isomers and after chlorination.What's more,both XPS and NEXAFS spectra show strong isomer dependence and the "fingerprint" in the X-ray spectra provide a valuable way to identify fullerene isomers.The simulated UV-vis absorption spectrum coincides with the previous experiment data.3.XPS,NEXAFS,UV-vis absorption spectrum as well as ground-state geometrical and electronic structures of recently captured non-IPR#6094C68 and the chlorinated derivative#6094C68Cl8 have been systematically studied.The ground state of Cs-C68 is open-shell triplet state possessing spherical aromaticity.Difference has been discovered both in electronic and geometrical structures after chlorination.Both X-ray spectra show strong isomer dependence and show a blue shift after chlorination.The simulated UV-vis absorption spectrum shows good agreement with the previous experimental data.The study broke up the normal mode that the most stable isomer usually exhibit singlet state in the investigation of fullerenes and thus play an important role in the further study of fullerenes and their derivatives.