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

Zhou, Qunfei; Liu, Zhen-Fei; Marks, Tobin J.; Darancet, Pierre

doi:10.1021/acs.jpca.0c10766

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

Journal Article · Fri May 07 00:00:00 UTC 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI: https://doi.org/10.1021/acs.jpca.0c10766 · OSTI ID:1798157

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Northwestern Univ., Evanston, IL (United States). Materials Research Science and Engineering Center; Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
Wayne State Univ., Detroit, MI (United States)
Northwestern Univ., Evanston, IL (United States). Materials Research Science and Engineering Center; Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Northwestern Argonne Inst. for Science and Engineering, Evanston, IL (United States)

In this work, 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 0.7 eV. Our comprehensive data set provides a new computational benchmark for gas-phase phthalocyanines, significantly improving upon other density-functional-theory-based approaches.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1798157

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 19 Vol. 125; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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