Electronic Structure of Metallophthalocyanines, MPc (M = Fe, Co, Ni, Cu, Zn, Mg) and Fluorinated MPc

27 October 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


We compute the electronic structure and optical excitation energies of metal-free and transition metal phthalocyanines (H2Pc and MPc for M = Fe, Co, Ni, Cu, Zn, Mg) using density functional

theory with optimally-tuned range-separated hybrid functionals (OT-RSH).We show that the OT-RSH approach provides photoemission spectra in quantitative agreement with experiments

as well as optical band gaps within 10% of their experimental values, capturing the interplay of localized d-states and delocalized pi-pi* states for these organometallic compounds. We examine the tunability of MPcs and H2Pc through fluorination, resulting in quasi-rigid shifts of the molecular orbital energies by up to about 0.7 eV. Our comprehensive dataset provides a new computational benchmark for phthalocyanines molecules, significantly improving upon other density-functional-theory-based approaches.


Electronic Structure
Transition Metal d Orbitals
Density Functional Theory
Optimally Tuned Range-Separated Hybrid Functional

Supplementary materials

MPc ElectrStr SI


Comments are not moderated before they are posted, but they can be removed by the site moderators if they are found to be in contravention of our Commenting Policy [opens in a new tab] - please read this policy before you post. Comments should be used for scholarly discussion of the content in question. You can find more information about how to use the commenting feature here [opens in a new tab] .
This site is protected by reCAPTCHA and the Google Privacy Policy [opens in a new tab] and Terms of Service [opens in a new tab] apply.