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Spin-state energetics of iron(II) porphyrin from the particle-particle random phase approximation

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Abstract

The particle-particle random phase approximation (pp-RPA) has been deployed to study the spin-state energetics of transition metal (TM) complexes for the first time in this work. Namely, we designed and implemented a non-canonical reference pp-RPA protocol that is capable of capturing the singlet low-spin (LS) – triplet intermediate-spin (IS) excitation process of iron(II) complexes; herein we applied this method to iron-porphyrin related heme derivatives with clearly defined LS and IS electronic states. Coupled to the CAM-B3LYP functional and to Dunning-type basis sets, we utilized both the active-space and Davidson methods to solve the pp-RPA equation effectively to obtain vertical singlet–triplet excitation energies. Correcting these vertical metrics with a structural relaxation factor for each species, we evaluated the relative stability of LS and IS electronic states. Comparison of the pp-RPA results to established ab initio data revealed that pp-RPA describes well excitation energies and related relative spin state stabilities if the transition is based on non-bonding d-orbitals, such as complexes without an axial ligand in the investigated set of molecules. But it notably overestimates the stability of the singlet LS state to the triplet IS state in complexes, where the d-orbitals at which the excitation is centered have bonding or antibonding character.

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Author information

Authors and Affiliations

  1. Departamento de Química, Universidad Técnica Federico Santa María, Valparaiso, 2390123, Chile

    Balazs Pinter

  2. Department of Chemistry, Duke University, Durham, NC, 27708, USA

    Balazs Pinter, Rachael Al-Saadon, Zehua Chen & Weitao Yang

  3. Department of General Chemistry, Free University of Brussels (VUB), Brussels, 1050, Belgium

    Balazs Pinter

  4. Department of Physics, Duke University, Durham, NC, 27708, USA

    Weitao Yang

  5. Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou, 510006, P.R. China

    Weitao Yang

Authors
  1. Balazs Pinter
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  2. Rachael Al-Saadon
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  3. Zehua Chen
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  4. Weitao Yang
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Corresponding author

Correspondence to Weitao Yang.

Additional information

Contribution to the Topical Issue “Special issue in honor of Hardy Gross”, edited by C.A. Ullrich, F.M.S. Nogueira, A. Rubio, and M.A.L. Marques.

Supplementary material in the form of one PDF file available from the Journal web page at https://doi.org/10.1140/epjb/e2018-90169-6

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Pinter, B., Al-Saadon, R., Chen, Z. et al. Spin-state energetics of iron(II) porphyrin from the particle-particle random phase approximation. Eur. Phys. J. B 91, 270 (2018). https://doi.org/10.1140/epjb/e2018-90169-6

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  • DOI: https://doi.org/10.1140/epjb/e2018-90169-6

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