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Electronic, bonding, and optical properties of 1d [ C u CN ] n ( n = 1–10) chains, 2d [ C u CN ] n ( n = 2–10) nanorings, and 3d [ C u n ( CN ) n ] m ( n = 4, m = 2, 3; n = 10, m = 2) tubes studied by DFT/TD‐DFT methods
Author(s) -
Tsipis Athanassios C.,
Stalikas Alexandros V.
Publication year - 2015
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.23932
Subject(s) - density functional theory , stacking , absorption spectroscopy , crystallography , absorption (acoustics) , chemistry , electronic structure , materials science , computational chemistry , physics , optics , organic chemistry , composite material
The electronic, bonding, and photophysical properties of one‐dimensional [CuCN] n ( n = 1–10) chains, 2‐D [CuCN] n ( n = 2–10) nanorings, and 3‐D [Cu n (CN) n ] m ( n = 4, m = 2, 3; n = 10, m = 2) tubes are investigated by means of a multitude of computational methodologies using density functional theory (DFT) and time‐dependent‐density‐functional theory (TD‐DFT) methods. The calculations revealed that the 2‐D [CuCN] n ( n = 2–10) nanorings are more stable than the respective 1‐D [CuCN] n ( n = 2–10) linear chains. The 2‐D [CuCN] n ( n = 2–10) nanorings are predicted to form 3‐D [Cu n (CN) n ] m ( n = 4, m = 2, 3; n = 10, m = 2) tubes supported by weak stacking interactions, which are clearly visualized as broad regions in real space by the 3D plots of the reduced density gradient. The bonding mechanism in the 1‐D [CuCN] n ( n = 1–10) chains, 2‐D [CuCN] n ( n = 2–10) nanorings, and 3‐D [Cu n (CN) n ] m ( n = 4, m = 2, 3; n = 10, m = 2) tubes are easily recognized by a multitude of electronic structure calculation approaches. Particular emphasis was given on the photophysical properties (absorption and emission spectra) of the [CuCN] n chains, nanorings, and tubes which were simulated by TD‐DFT calculations. The absorption and emission bands in the simulated TD‐DFT absorption and emission spectra have thoroughly been analyzed and assignments of the contributing principal electronic transitions associated to individual excitations have been made. © 2015 Wiley Periodicals, Inc.