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DFT assessment of the spectroscopic constants and absorption spectra of neutral and charged diatomic species of group 11 and 14 elements

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Abstract

The spectroscopic constants and absorption spectra of neutral and charged diatomic molecules of group 11 and 14 elements formulated as [M2]+/0/− (M = Cu, Ag, Au), and [E2]+/0/− (E = C, Si, Ge, Sn, Pb) have been calculated at the PBE0/Def2-QZVPP level of theory. The electronic and bonding properties of the diatomics have been analyzed by natural bond orbital analysis approach and topology analysis by the atoms in molecules method. Particular emphasis was given on the absorption spectra of the diatomic species, which were simulated by time-dependent density functional theory calculations employing the hybrid Coulomb-attenuating CAM-B3LYP density functional. The simulated absorption spectra of the [M2]+/0/− (M = Cu, Ag, Au) and [E2]+/0/− (E = C, Si, Ge, Sn, Pb) species are in close resemblance with the experimentally observed spectra whenever available. The neutral M2 and E2 diatomics strongly absorb in the ultraviolet region, given rise to UVC, UVA and in a few cases UVB absorptions. In a few cases, weak absorbion bands also occur in the visible region. The absorption bands have thoroughly been analyzed and assignments of the contributing principal electronic transitions associated to individual excitations have been made. © 2014 Wiley Periodicals, Inc.

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