Spin states of Mn(III) meso-tetraphenylporphyrin chloride assessed by density functional methods


The present work assessed several exchange-correlation functionals (including GGA, meta-GGA and hybrid functionals), in combination with a variety of basis sets and effective core potentials (ECP) for their ability to predict the ground spin state of Mn(III) meso-tetraphenylporphyrin chloride complex, labeled Mn(III)TPPCl, for which experimental data support the quintet high spin state. Geometry optimization of Mn(III)TPPCl was performed for three possible spin states (singlet state, LS; triplet state, IS; and quintet state, HS) at the TPSSh level using the LANL2DZ ECP for Mn and the 6-311G(d) basis set for C, N, Cl and H. Afterwards, single-point energy calculations were conducted by applying 18 exchange-correlation functionals (BLYP, B3LYP, PW91, BPW91, BP86, OLYP, OPBE, OPW91, O3LYP, PBE0, PBEh1PBE, HSEH1PBE, TPSS, TPSSh, M06 L, M06, M062X and M06HF). The influence of the basis set for the metal center was assessed using a smaller group of functionals and varying between the Pople basis set 6-31G(d), its newer formulation m6-31G(d) and the larger Def2-QZVP basis set. All functionals in combination with Pople basis sets predict the quintet state as the ground spin state. In addition, the BLYP, BP86, BPW91, PW91, PBEh1PBE, TPSS and TPSSh functionals predicted the IS lying at most ~60 kJ mol−1 above the HS, which agrees with the reference data. Results including Def2-QZVP basis set were inconsistent, since only BLYP and B3LYP predict HS as the ground spin state. The recommended methodology for the treatment of such systems seems to be exchange-correlations functionals with few or none Hartree-Fock exchange and modest size basis sets.

MnTPPCl molecule and the energy ordering of its spin states assessed by 18 functionals

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The authors gratefully acknowledge the financial support from the Brazilian agencies, institutes and networks: Instituto Nacional de Ciência e Tecnologia de Nanotecnologia para Marcadores Integrados (INCT-INAMI), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES), Programa de Apoio a Núcleos de Excelência (PRONEX-FACEPE) and Financiadora de Estudos e Projetos (FINEP). The authors also acknowledge the physical structure and computational support provided by Universidade Federal da Paraíba (UFPB) and Instituto Federal de Educação, Ciência e Tecnologia da Paraíba (IFPB) and the computer resources of Centro Nacional de Processamento de Alto Desempenho em São Paulo (CENAPAD-SP).

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de Lima Bezerra Cavalcanti, H., Bruno Rocha, G. Spin states of Mn(III) meso-tetraphenylporphyrin chloride assessed by density functional methods. J Mol Model 23, 363 (2017). https://doi.org/10.1007/s00894-017-3515-5

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  • DFT
  • Mn porphyrins
  • Metalloporphyrins
  • Spin state