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

Malcioglu O, Bechis I, Bockstedte MG (2020)

Publication Type: Journal article

Publication year: 2020

Journal

Physical Chemistry Chemical Physics Royal Society of Chemistry

Book Volume: 22

Pages Range: 3825-3830

Journal Issue: 7

DOI: 10.1039/c9cp06040e

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.

Authors with CRIS profile

Osman Malcioglu Lehrstuhl für Theoretische Festkörperphysik Michel Georg Bockstedte Lehrstuhl für Theoretische Festkörperphysik

Involved external institutions

Universität Salzburg (Paris Lodron Universität Salzburg)

Austria (AT)

How to cite

APA:

Malcioglu, O., Bechis, I., & Bockstedte, M.G. (2020). Effect of crystallization on the electronic and optical properties of archetypical porphyrins. Physical Chemistry Chemical Physics, 22(7), 3825-3830. https://dx.doi.org/10.1039/c9cp06040e

MLA:

Malcioglu, Osman, Irene Bechis, and Michel Georg Bockstedte. "Effect of crystallization on the electronic and optical properties of archetypical porphyrins." Physical Chemistry Chemical Physics 22.7 (2020): 3825-3830.

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