Seyed Hassan Nabavi, Mohammad Hassan Khodabandeh, Maryam Golbabaee, Ahmad Moshaii,
Volume 12, Issue 1 (1-2018)
Experimental and theoretical absorption spectra of [2-[2-[4-(dimethylamino) phenyl]ethenyl]-6-methyl-4H- pyran-4-ylidene]-propanedinitrile (DCM) have been studied. UV-Visible (UV-Vis.) absorption spectrum of DCM has been reported after its synthesis. Two relatively intense peaks appeared at 473 and 362 nm respectively. A theoretical investigation on the electronic structure of DCM is presented in an effort to rationalize our experimental results. Theoretical results have been obtained with a polarizable continuum model time-dependent density functional theory (PCM-TD-DFT) approach. At first, a vast functional benchmark has been performed to determine a suitable approach for determination of electronic structure and UV-Vis. absorption spectrum of DCM. In a second step, we evaluated the impact of the atomic basis set on the electronic transition energies using a large panel of Pople’s basis sets ,up to the 6-31+G(3df,2p) and also a correlation consistent basis set, cc-pVTZ. It turns out that the selected basis set has a relatively finite influence on the calculated electronic transition energies as well as the topology of the absorption shape, but both are significantly affected by the chosen functional. In the present case, no single functional simultaneously provides highly accurate positions and intensities of the different bands, but mPW1PBE and mPW1LYP appear to be a good compromise. The mPW1PBE along with medium basis sets produced both absorption bands with maximum peaks about 463 and 346 nm. At all stages, ethanol has been chosen as a solvent environment. To improve the accuracy of first electronic excitation, a complete analysis of the origin of the band shape using TD-DFT vibrational couplings was performed. Finally the computed transition energy was corrected to 472 nm which was in excellent agreement with experiments.
