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Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers

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Abstract

The relationship between structure and photo electrochemical property of ten natural pigments from plants, insects and microbes has been analyzed using density functional theory (DFT) at the B3LYP/6-31G(d) level. The essential parameters for their photoelectrochemical behaviour such as ground state geometries, electronic transition energies and oxidation potentials are computed. The attachment tendency of the anchoring groups, expressed as the deprotonation order, is determined by calculating the proton affinities at different sites of the molecules. A thorough analysis of the charge flow dynamics in the molecular orbitals (HOMO and LUMO) of these molecules has been carried out and presented to emphasize the role of these orbitals in effective charge separation, the important feature of photosensitizers for DSSC. This study highlights that the flexible spatial orientation provided by the bridging aliphatic unsaturation favours the oscillator strength and the hydroxyl anchor group attached to the ring of delocalized π electron cloud acts as the effective anchor.

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Acknowledgments

The authors thank Prof. M. Chidambaram, Director, NITT, India, for creating the computational Chemistry Lab. facilities for carrying out this work.

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  1. Department of Chemistry, National Institute of Technology, Tiruchirappalli, 620015, India

    Thekinneydath Rajan Heera & Louis Cindrella

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  1. Thekinneydath Rajan Heera
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  2. Louis Cindrella
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Correspondence to Louis Cindrella.

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Heera, T.R., Cindrella, L. Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers. J Mol Model 16, 523–533 (2010). https://doi.org/10.1007/s00894-009-0569-z

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