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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
Author(s) -
Tsipis Athanassios C.
Publication year - 2014
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.23684
Subject(s) - diatomic molecule , chemistry , absorption spectroscopy , density functional theory , spectral line , absorption (acoustics) , atomic physics , molecule , computational chemistry , molecular physics , materials science , physics , quantum mechanics , organic chemistry , composite material
The spectroscopic constants and absorption spectra of neutral and charged diatomic molecules of group 11 and 14 elements formulated as [M 2 ] +/0/− (M = Cu, Ag, Au), and [E 2 ] +/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 [M 2 ] +/0/− (M = Cu, Ag, Au) and [E 2 ] +/0/− (E = C, Si, Ge, Sn, Pb) species are in close resemblance with the experimentally observed spectra whenever available. The neutral M 2 and E 2 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.