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Theoretical investigation of structure diversity and electronic properties in the series isomeric [26]hexaphyrin (1.1.1.1.1.1) and [28]hexaphyrin (1.1.1.1.1.1)
- Source :
- Computational and Theoretical Chemistry. 1087:18-25
- Publication Year :
- 2016
- Publisher :
- Elsevier BV, 2016.
-
Abstract
- In this work, [26]hexaphyrin (1.1.1.1.1.1) and corresponding [28]hexaphyrin (1.1.1.1.1.1) with different structures have been investigated using density functional theory (DFT) and time-dependent DFT. The frontier molecular orbitals (FMOs), aromaticity, electronic spectra and nonlinear optical properties were systematically investigated. Significantly, thienyls groups on the meso -carbon have great influence on the electronic properties. Based on an analysis of orbital composition, contribution of the thienyls to FMOs concentrates primarily on HOMO and third highest occupied molecular orbital (HOMO−2) to aromatic molecules, and focuses on second highest occupied molecular orbital (HOMO−1) to antiaromatic molecules. In addition, the first hyperpolarizability ( β 0 ) values of dumbbell-shape and rectangular-shape molecules are significantly lower than those of the other three molecules. For the other three molecules with both aromatic molecules and antiaromatic molecules, their β 0 values have the same regularities that are in the orders of triangular-shape β 0 value of antiaromatic molecules is greater than that of aromatic molecules because of their different transition properties. We hope that this work will provide valuable information for adjusting electro-optical properties by changing substituent group on the meso -carbon, aromaticity and configuration.
- Subjects :
- 010405 organic chemistry
Chemistry
Hyperpolarizability
Aromaticity
Time-dependent density functional theory
010402 general chemistry
Condensed Matter Physics
01 natural sciences
Biochemistry
0104 chemical sciences
Computational chemistry
Molecule
Density functional theory
Molecular orbital
Physical and Theoretical Chemistry
HOMO/LUMO
Antiaromaticity
Subjects
Details
- ISSN :
- 2210271X
- Volume :
- 1087
- Database :
- OpenAIRE
- Journal :
- Computational and Theoretical Chemistry
- Accession number :
- edsair.doi...........d8075c4efa357c46d10af77a7d3d7f5e