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Investigating functional performance and substituent effect in modelling molecular structure, UV-visible spectra, and optical properties of D-π-A conjugated organic dye molecules: a DFT and TD-DFT study

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Abstract

The molecular structure, UV-visible spectra, and optical properties of D-π-A conjugated organic dye molecules (Disperse Red 1 (DR1) and Disperse Red 73 (DR73)) were analyzed using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) and compared with azobenzene molecule to study the effect of donor and acceptor substituents on the molecular properties. The performance of DFT functionals is investigated using B3LYP hybrid functional and three long-range corrected functionals (CAM-B3LYP, LC-ω PBE, and ω B97XD) in conjunction with 6-31G(d,p) basis set. Using TD-DFT, we calculate the vertical excitation energies and transition dipole moment values for 100 excited states. These values were further utilized to calculate frequency dependent polarizability under sum-over-states (SOS) formalism and refractive index of these molecular systems. We observe that for azobenzene and DR1 molecules, ω B97XD predicted wavelengths corresponding to peak absorbance closest to the experimental results, while for DR73 molecule, B3LYP gave better prediction. Large polarizability response is also observed for these molecules (DR1 and DR73) in comparison to parent azobenzene structure due to charge transfer between donor and acceptor groups. For DR1 and DR73 molecules, αxx component of polarizability dominates in contrast to azobenzene where αyy dominates. The HOMO → LUMO transition during excitation contributes to the peak molecular response in simulated UV-visible spectra. The high polarizability response of selected D-π-A conjugated molecules in comparison to parent molecule suggests that these molecules are promising candidates for tailor-made photonic and optoelectronic device development.

Functional and substituent effect on the optical response of D-π-A conjugated molecules modelled using DFT and TDDFT.

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Acknowledgements

Dr. Kriti Batra is thankful to Guru Gobind Singh Indraprastha University for research grant under the Faculty Research Grant Scheme (FRGS) for the year 2019-20 (F.No. GGSIPU/DRC/FRGS/2019/1553/12). Garima Chanana is grateful to Guru Gobind Singh Indraprastha University for providing financial support under Short Term Research Fellowship (STRF) scheme (L.No GGSIPU/DRC/Ph.D./2018/1288)

Funding

This study was financially supported by Guru Gobind Singh Indraprastha University.

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    Garima Chanana & Kriti Batra

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Dr. Kriti Batra: Conceptualization of idea of study, software implementation of computer code, formal analysis, provision of resources, supervision, review and editing the draft, project administration, and funding acquisition. Garima Chanana: validation of results, investigation–performing calculations, data curation-maintaining research data for initial and final use, writing original draft preparation, visualization–presentation of results.

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Chanana, G., Batra, K. Investigating functional performance and substituent effect in modelling molecular structure, UV-visible spectra, and optical properties of D-π-A conjugated organic dye molecules: a DFT and TD-DFT study. J Mol Model 27, 229 (2021). https://doi.org/10.1007/s00894-021-04824-y

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