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Electronic structures and nonlinear optical properties of highly deformed halofullerenes C 3 v C 60 F 18 and D 3 d C 60 Cl 30
Author(s) -
Tang ShuWei,
Feng JingDong,
Qiu YongQing,
Sun Hao,
Wang FengDi,
Chang YingFei,
Wang RongShun
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21560
Subject(s) - hyperpolarizability , delocalized electron , polarizability , atomic orbital , halogen , electron , chemistry , crystallography , density functional theory , molecular orbital , electronic structure , ring (chemistry) , chemical shift , atomic physics , molecular physics , physics , materials science , computational chemistry , molecule , organic chemistry , quantum mechanics , alkyl
Electronic structures and nonlinear optical properties of two highly deformed halofullerenes C 3 v C 60 F 18 and D 3 d 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 $ \left\langle \alpha \right\rangle $ and second‐order hyperpolarizability $ \left\langle \gamma \right\rangle $ of C 60 F 18 and C 60 Cl 30 are calculated using finite‐field approach. The values of $ \left\langle \alpha \right\rangle $ and $ \left\langle \gamma \right\rangle $ 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 π electrons. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010