Density functional theory (DFT) investigations on doped fullerene with heteroatom substitution

•Structure, stabilities of dodecahedral fullerene C19X (X = Ni, Ti) and C20 have been investigated.•Quantum chemical calculations have been performed on the basis of DFT.•The doping effect is discussed in terms of the change in the CC bond length.•Electronic, optical properties, band gap, vibrational frequency have been calculated.

Structures and stabilities of dodecahedral fullerene C19X (X = Ni, Ti) and C20 have been investigated by quantum chemical calculations based on density functional theory. The geometrical structures, relative stabilities, dielectric constant of the doped cages were studied systematically and compared with those of the fullerene C20 cage. A series of dodecahedral functionalized derivatives have been studied at the B3LYP/6-31G level of density functional theory (DFT). The relative and formation energies of compounds, Mulliken charges, occupancy, the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), the HOMO–LUMO band gap and chemical potential (μ) were calculated. The doping effect is discussed in terms of the change in the CC bond length and total dipole moment. The obtained result indicates that the CC bond length increases as a result of doping. The NBO analysis showed that there is a hyper conjugative interaction between the hetero atoms such as titanium and nickel lone-pair electron of doped fullerene with bonding and antibonding (σ∗) orbital of carbon atom of fullerene. The stability of the molecule, arising from charge delocalization, has been analyzed using Natural Bond Orbital (NBO) analysis. The nucleus – independent that more negative NICS values in doped fullerene than those of C20. The condensed Fukui Function and the newly introduced the atomic descriptors S (fk) to determine the local reactive sites of the molecular systems during electrophilic, nucleophilic and radical attacks have been calculated for the fullerene C20 compound.

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