Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope
The optical properties of a series of donor-acceptor N,N-dimethylaniline-π-dicyanovinylene (DMA-π-DCV) chromophores have been investigated under the density functional theory framework. Focus has been made on the low-lying charge-transfer (CT) electronic transitions for which experimental data is av...
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2016-01-01
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| Series: | Journal of Spectroscopy |
| Online Access: | http://dx.doi.org/10.1155/2016/3520698 |
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| author | Joaquín Calbo |
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| description | The optical properties of a series of donor-acceptor N,N-dimethylaniline-π-dicyanovinylene (DMA-π-DCV) chromophores have been investigated under the density functional theory framework. Focus has been made on the low-lying charge-transfer (CT) electronic transitions for which experimental data is available. The effect of the π-conjugated bridge length and type was analysed between the families of oligoene and oligoyne derivatives of increasing size. Theoretical calculations demonstrate that the ethylene bridge is a better π-communicator and allows for more delocalized frontier molecular orbitals compared to the acetylene spacer. The Λ diagnostic test allowed rationalization of the orbital spatial overlap in the main CT excitations. The performance of different density functional rungs was assessed in the prediction of the lowest-lying CT electronic transition. Surprisingly, most modern long-range corrected functionals demonstrated to provide among the largest errors, whereas hybrid functionals showed the best performance. Solvatochromism was confirmed in both oligoene and oligoyne compounds. A donor-acceptor-donor triad based on tetrathiafulvalene was utilised as a test system for the prediction of its two CT bands of different nature, energy, and intensity. The hybrid PBE0 (or a similar hybrid analogue) consolidates as the best choice for the prediction of CT excitations in the DMA-π-DCV push-pull family. |
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| institution | Kabale University |
| issn | 2314-4920 2314-4939 |
| language | English |
| publishDate | 2016-01-01 |
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| series | Journal of Spectroscopy |
| spelling | doaj-art-be2ae6437ff34d41951393f4e68c31252025-02-03T05:43:44ZengWileyJournal of Spectroscopy2314-49202314-49392016-01-01201610.1155/2016/35206983520698Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT MicroscopeJoaquín Calbo0Instituto de Ciencia Molecular, Universidad de Valencia, 46890 Paterna, SpainThe optical properties of a series of donor-acceptor N,N-dimethylaniline-π-dicyanovinylene (DMA-π-DCV) chromophores have been investigated under the density functional theory framework. Focus has been made on the low-lying charge-transfer (CT) electronic transitions for which experimental data is available. The effect of the π-conjugated bridge length and type was analysed between the families of oligoene and oligoyne derivatives of increasing size. Theoretical calculations demonstrate that the ethylene bridge is a better π-communicator and allows for more delocalized frontier molecular orbitals compared to the acetylene spacer. The Λ diagnostic test allowed rationalization of the orbital spatial overlap in the main CT excitations. The performance of different density functional rungs was assessed in the prediction of the lowest-lying CT electronic transition. Surprisingly, most modern long-range corrected functionals demonstrated to provide among the largest errors, whereas hybrid functionals showed the best performance. Solvatochromism was confirmed in both oligoene and oligoyne compounds. A donor-acceptor-donor triad based on tetrathiafulvalene was utilised as a test system for the prediction of its two CT bands of different nature, energy, and intensity. The hybrid PBE0 (or a similar hybrid analogue) consolidates as the best choice for the prediction of CT excitations in the DMA-π-DCV push-pull family.http://dx.doi.org/10.1155/2016/3520698 |
| spellingShingle | Joaquín Calbo Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope Journal of Spectroscopy |
| title | Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope |
| title_full | Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope |
| title_fullStr | Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope |
| title_full_unstemmed | Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope |
| title_short | Optical Properties of DMA-π-DCV Derivatives: A Theoretical Inspection under the DFT Microscope |
| title_sort | optical properties of dma π dcv derivatives a theoretical inspection under the dft microscope |
| url | http://dx.doi.org/10.1155/2016/3520698 |
| work_keys_str_mv | AT joaquincalbo opticalpropertiesofdmapdcvderivativesatheoreticalinspectionunderthedftmicroscope |