Density Functional Studies of Molecular Polarizabilities. 10. Fulvenes and Fulvalenes

International Journal of Molecular Sciences

Alan Hinchliffe¹ 

[1] Department of Chemistry, UMIST, Sackville Street, Manchester M60 1QD, UK Tel.: [phone], Fax: [phone], E-mail:

关键词: Ab Initio;    dipole polarizability;    dipole hyperpolarizability;    molecular geometry;    density functional theory;    fulvenes;    fulvalenes;    cyclopropene;    cyclopentadiene;    cycloheptatriene;   

DOI  :  10.3390/ijms1030039

来源: mdpi

【 摘 要 】

We report accurate Ab Initio Hartree Fock (HF) and Density Functional Theory (DFT) studies of the static dipole polarizabilities and first hyperpolarizabilities of the [n] fulvene and the [n,m] fulvalene series of molecules (with n, m = 3,5,7). Calculations are also reported for the parent cycloalkenes: cyclopropene, cyclopentadiene and cycloheptatriene (1-3 respectively). Geometries were optimized at the HF/6-311G(3d,2p) level of theory. All the fulvenes (4-6) and the smaller fulvalenes (7, 9 and 10) are found to be planar. Pentaheptafulvalene (11) is slightly non-planar whilst heptafulvalene (12) has a folded C_2h structure. Calculated C-C bond lengths are consistently smaller than the experimental values. Dipole polarizabilities and non-zero hyperpolarizabilities were calculated at the HF/6311++G(3d,2p) and BLYP/6-311++G(3d,2p) levels of theory, using HF/6-311G(3d,2p) geometries. Dipole polarizabilities correlate well with those given on the basis of atom additivity. Molecules (8), (9) and (11) show very large dipole hyperpolarizabilities.

【 授权许可】

Unknown   
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