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Issue 7, 2020
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Effect of crystallization on the electronic and optical properties of archetypical porphyrins

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Abstract

Thin porphyrin films as employed in modern optical devices or photovoltaic applications show deviating electronic and optical properties from the gasphase species. Any understanding of the physical origin may pave way to a specific engineering of these properties via ligand or substituent control. Here we investigate the impact of crystallization of prototypical porphyrins on the electronic levels and optical properties in the framework of density functional theory and many-body perturbation theory. Crystallization substantially shrinks the HOMO–LUMO gap based on polarization effects. We find a shift of the HOMO to higher energy is consistent with recent experiment of MgTPP multilayer film on Ag (100) [A. Classen et al., Phys. Rev. B, 2017, 95, 115414]. Calculated excitation spectra demonstrate a significant redshift of excitation bands except for the Q bands. These lowest excitation bands, in stark contrast to the strong HOMO–LUMO gap renormalization, remain essentially the same as in the gas phase. Our work underlines the possibility of band-gap engineering via ligand-controlled modification of the polarizability.

Graphical abstract: Effect of crystallization on the electronic and optical properties of archetypical porphyrins

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Supplementary files

Article information


Submitted
06 Nov 2019
Accepted
21 Jan 2020
First published
21 Jan 2020

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 3825-3830
Article type
Paper

Effect of crystallization on the electronic and optical properties of archetypical porphyrins

O. B. Malcıoğlu, I. Bechis and M. Bockstedte, Phys. Chem. Chem. Phys., 2020, 22, 3825
DOI: 10.1039/C9CP06040E

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