title: Electronic structures and nonlinear optical properties of highly deformed halofullerenes C(3v) C60F18 and D(3d) C60Cl30.
abstract: Electronic structures and nonlinear optical properties of two highly deformed halofullerenes C(3v) C(60)F(18) and D(3d) C(60)Cl(30) have been systematically studied by means of density functional theory. The large energy gaps (3.62 and 2.61 eV) between the highest occupied and lowest unoccupied molecular orbitals (HOMOs and LUMOs) and the strong aromatic character (with nucleus-independent chemical shifts varying from -15.08 to -23.71 ppm) of C(60)F(18) and C(60)Cl(30) indicate their high stabilities. Further investigations of electronic property show that C(60)F(18) and C(60)Cl(30) could be excellent electron acceptors for potential photonic/photovoltaic applications in consequence of their large vertical electron affinities. The density of states and frontier molecular orbitals are also calculated, which present that HOMOs and LUMOs are mainly distributed in the tortoise shell subunit of C(60)F(18) and the aromatic [18] trannulene ring of C(60)Cl(30), and the influence from halogen atoms is secondary. In addition, the static linear polarizability <alpha> and second-order hyperpolarizability <gamma> of C(60)F(18) and C(60)Cl(30) are calculated using finite-field approach. The values of <alpha> and <gamma> for C(60)F(18) and C(60)Cl(30) molecules are significantly larger than those of C(60) because of their lower symmetric structures and high delocalization of pi electrons.
authors.affiliation: Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin 130024, People's Republic of China.
authors.forename: Shu-Wei
authors.initials: SW
authors.lastname: Tang
authors.forename: Jing-Dong
authors.initials: JD
authors.lastname: Feng
authors.forename: Yong-Qing
authors.initials: YQ
authors.lastname: Qiu
authors.forename: Hao
authors.initials: H
authors.lastname: Sun
authors.forename: Feng-Di
authors.initials: FD
authors.lastname: Wang
authors.forename: Ying-Fei
authors.initials: YF
authors.lastname: Chang
authors.forename: Rong-Shun
authors.initials: RS
authors.lastname: Wang
mesh_terms: D004583:Electrons; D037741:Fullerenes / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D055095:Optics and Photonics; D011789:Quantum Theory
chemical_list: D037741:Fullerenes