Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes

X. G. Zhao, W. H. Richardson, J. L. Chen, J. Li, L. Noodleman, Hui-Lien Tsai, D. N. Hendrickson

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Abstract

We have calculated the electronic structures of five different manganese-oxo dimer complexes using density functional methods combined with the broken symmetry and spin projection concepts. The number of carboxylate, oxo, and peroxo bridging ligands was varied, and the terminal ligands were triazacyclononane (TACN). The formal Mn oxidation states varied from MnIII2 and MnIIIMnIV to MnIV2. These complexes have been synthesized and their X-ray structures and magnetic properties measured previously. We have calculated the Heisenberg spin coupling parameters J and resonance delocalization parameters B for all of these systems. Despite the very small energy differences involved, there is a good correspondence between calculated and experimental Heisenberg J parameters. We have analyzed potential changes in the calculated effective Heisenberg coupling Jeff for the mixed-valence MnIIIMnIV complexes when partial or complete delocalization due to the B parameter is taken into account. These changes depend also on the energy of the relevant intervalence band. Surprisingly, in the two mixed-valence systems studied, the high spin S = 5/2 state lies below S = 7/2. This is consistent with spin coupling between Mn with site spins S1 = 1, S2 =3/2 corresponding to intermediate spin Mn(I) and Mn(II) respectively, instead of the coupling expected from the formal oxidation states, S1 = 2, S2 = 3/2 from high spin Mn(III) and Mn(IV). The spin and charge distributions in the broken symmetry ground states are also consistent with intermediate spin S1 = 1, S2 = 3/2. The calculated charge distributions show strong metal-ligand covalency. In fact, as the formal oxidation states of the Mn sites increase, the net Mn charges generally show a slow decrease, consistent with a very strong ligand → metal charge transfer, particularly from μ-oxo or μ-peroxo ligands. TACN is a better donor ligand than carboxylate, even when calculated on a per donor atom basis. The ligand atom charge transfer order is peroxo ≥ oxo ≫ TACN > acetate. The TACN > acetate ordering is expected from the spectrochemical series, but the strong charge transfer and strong metal - ligand covalency of peroxo and oxo ligands with the Mn sites cannot be simply related to their positions in the spectrochemical series. In the MnIV2(μ-O)2(μ-O2)(TACN) 2, each peroxo oxygen has a small charge (-0.3), much less than found for each μ-O atom (-0.7). The high-spin S = 3 state lies quite low in energy, 8 kcal/mol from our calculations and about 4 kcal/mol based on the experimental Heisenberg spin coupling parameters. Potential molecular oxygen dissociation pathways involving a spin S = 1 state are discussed. Effective ligand field diagrams are constructed from the calculated energy levels which display the competition between spin polarization splitting and the ligand field t2g - eg splitting and allow comparisons of electronic structure among different complexes. The electronic structure and spin coupling of these complexes was also compared to the corresponding "core-only" complexes where both TACN ligands were removed, yielding a far weaker ligand field. There is a strong ferromagnetic shift in the "core-only" complexes compared with the complete TACN complexes, also showing the effects of a weaker ligand field.

Original languageEnglish
Pages (from-to)1198-1217
Number of pages20
JournalInorganic Chemistry
Volume36
Issue number6
Publication statusPublished - 1997 Dec 1

Fingerprint

Charge distribution
Manganese
Dimers
charge distribution
Electronic structure
Density functional theory
manganese
dimers
electronic structure
Ligands
ligands
Charge transfer
Metals
charge transfer
Atoms
Oxidation
carboxylates
oxidation
acetates
broken symmetry

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Zhao, X. G., Richardson, W. H., Chen, J. L., Li, J., Noodleman, L., Tsai, H-L., & Hendrickson, D. N. (1997). Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes. Inorganic Chemistry, 36(6), 1198-1217.
Zhao, X. G. ; Richardson, W. H. ; Chen, J. L. ; Li, J. ; Noodleman, L. ; Tsai, Hui-Lien ; Hendrickson, D. N. / Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes. In: Inorganic Chemistry. 1997 ; Vol. 36, No. 6. pp. 1198-1217.
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abstract = "We have calculated the electronic structures of five different manganese-oxo dimer complexes using density functional methods combined with the broken symmetry and spin projection concepts. The number of carboxylate, oxo, and peroxo bridging ligands was varied, and the terminal ligands were triazacyclononane (TACN). The formal Mn oxidation states varied from MnIII2 and MnIIIMnIV to MnIV2. These complexes have been synthesized and their X-ray structures and magnetic properties measured previously. We have calculated the Heisenberg spin coupling parameters J and resonance delocalization parameters B for all of these systems. Despite the very small energy differences involved, there is a good correspondence between calculated and experimental Heisenberg J parameters. We have analyzed potential changes in the calculated effective Heisenberg coupling Jeff for the mixed-valence MnIIIMnIV complexes when partial or complete delocalization due to the B parameter is taken into account. These changes depend also on the energy of the relevant intervalence band. Surprisingly, in the two mixed-valence systems studied, the high spin S = 5/2 state lies below S = 7/2. This is consistent with spin coupling between Mn with site spins S1 = 1, S2 =3/2 corresponding to intermediate spin Mn(I) and Mn(II) respectively, instead of the coupling expected from the formal oxidation states, S1 = 2, S2 = 3/2 from high spin Mn(III) and Mn(IV). The spin and charge distributions in the broken symmetry ground states are also consistent with intermediate spin S1 = 1, S2 = 3/2. The calculated charge distributions show strong metal-ligand covalency. In fact, as the formal oxidation states of the Mn sites increase, the net Mn charges generally show a slow decrease, consistent with a very strong ligand → metal charge transfer, particularly from μ-oxo or μ-peroxo ligands. TACN is a better donor ligand than carboxylate, even when calculated on a per donor atom basis. The ligand atom charge transfer order is peroxo ≥ oxo ≫ TACN > acetate. The TACN > acetate ordering is expected from the spectrochemical series, but the strong charge transfer and strong metal - ligand covalency of peroxo and oxo ligands with the Mn sites cannot be simply related to their positions in the spectrochemical series. In the MnIV2(μ-O)2(μ-O2)(TACN) 2, each peroxo oxygen has a small charge (-0.3), much less than found for each μ-O atom (-0.7). The high-spin S = 3 state lies quite low in energy, 8 kcal/mol from our calculations and about 4 kcal/mol based on the experimental Heisenberg spin coupling parameters. Potential molecular oxygen dissociation pathways involving a spin S = 1 state are discussed. Effective ligand field diagrams are constructed from the calculated energy levels which display the competition between spin polarization splitting and the ligand field t2g - eg splitting and allow comparisons of electronic structure among different complexes. The electronic structure and spin coupling of these complexes was also compared to the corresponding {"}core-only{"} complexes where both TACN ligands were removed, yielding a far weaker ligand field. There is a strong ferromagnetic shift in the {"}core-only{"} complexes compared with the complete TACN complexes, also showing the effects of a weaker ligand field.",
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Zhao, XG, Richardson, WH, Chen, JL, Li, J, Noodleman, L, Tsai, H-L & Hendrickson, DN 1997, 'Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes', Inorganic Chemistry, vol. 36, no. 6, pp. 1198-1217.

Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes. / Zhao, X. G.; Richardson, W. H.; Chen, J. L.; Li, J.; Noodleman, L.; Tsai, Hui-Lien; Hendrickson, D. N.

In: Inorganic Chemistry, Vol. 36, No. 6, 01.12.1997, p. 1198-1217.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Density Functional Calculations of Electronic Structure, Charge Distribution, and Spin Coupling in Manganese-Oxo Dimer Complexes

AU - Zhao, X. G.

AU - Richardson, W. H.

AU - Chen, J. L.

AU - Li, J.

AU - Noodleman, L.

AU - Tsai, Hui-Lien

AU - Hendrickson, D. N.

PY - 1997/12/1

Y1 - 1997/12/1

N2 - We have calculated the electronic structures of five different manganese-oxo dimer complexes using density functional methods combined with the broken symmetry and spin projection concepts. The number of carboxylate, oxo, and peroxo bridging ligands was varied, and the terminal ligands were triazacyclononane (TACN). The formal Mn oxidation states varied from MnIII2 and MnIIIMnIV to MnIV2. These complexes have been synthesized and their X-ray structures and magnetic properties measured previously. We have calculated the Heisenberg spin coupling parameters J and resonance delocalization parameters B for all of these systems. Despite the very small energy differences involved, there is a good correspondence between calculated and experimental Heisenberg J parameters. We have analyzed potential changes in the calculated effective Heisenberg coupling Jeff for the mixed-valence MnIIIMnIV complexes when partial or complete delocalization due to the B parameter is taken into account. These changes depend also on the energy of the relevant intervalence band. Surprisingly, in the two mixed-valence systems studied, the high spin S = 5/2 state lies below S = 7/2. This is consistent with spin coupling between Mn with site spins S1 = 1, S2 =3/2 corresponding to intermediate spin Mn(I) and Mn(II) respectively, instead of the coupling expected from the formal oxidation states, S1 = 2, S2 = 3/2 from high spin Mn(III) and Mn(IV). The spin and charge distributions in the broken symmetry ground states are also consistent with intermediate spin S1 = 1, S2 = 3/2. The calculated charge distributions show strong metal-ligand covalency. In fact, as the formal oxidation states of the Mn sites increase, the net Mn charges generally show a slow decrease, consistent with a very strong ligand → metal charge transfer, particularly from μ-oxo or μ-peroxo ligands. TACN is a better donor ligand than carboxylate, even when calculated on a per donor atom basis. The ligand atom charge transfer order is peroxo ≥ oxo ≫ TACN > acetate. The TACN > acetate ordering is expected from the spectrochemical series, but the strong charge transfer and strong metal - ligand covalency of peroxo and oxo ligands with the Mn sites cannot be simply related to their positions in the spectrochemical series. In the MnIV2(μ-O)2(μ-O2)(TACN) 2, each peroxo oxygen has a small charge (-0.3), much less than found for each μ-O atom (-0.7). The high-spin S = 3 state lies quite low in energy, 8 kcal/mol from our calculations and about 4 kcal/mol based on the experimental Heisenberg spin coupling parameters. Potential molecular oxygen dissociation pathways involving a spin S = 1 state are discussed. Effective ligand field diagrams are constructed from the calculated energy levels which display the competition between spin polarization splitting and the ligand field t2g - eg splitting and allow comparisons of electronic structure among different complexes. The electronic structure and spin coupling of these complexes was also compared to the corresponding "core-only" complexes where both TACN ligands were removed, yielding a far weaker ligand field. There is a strong ferromagnetic shift in the "core-only" complexes compared with the complete TACN complexes, also showing the effects of a weaker ligand field.

AB - We have calculated the electronic structures of five different manganese-oxo dimer complexes using density functional methods combined with the broken symmetry and spin projection concepts. The number of carboxylate, oxo, and peroxo bridging ligands was varied, and the terminal ligands were triazacyclononane (TACN). The formal Mn oxidation states varied from MnIII2 and MnIIIMnIV to MnIV2. These complexes have been synthesized and their X-ray structures and magnetic properties measured previously. We have calculated the Heisenberg spin coupling parameters J and resonance delocalization parameters B for all of these systems. Despite the very small energy differences involved, there is a good correspondence between calculated and experimental Heisenberg J parameters. We have analyzed potential changes in the calculated effective Heisenberg coupling Jeff for the mixed-valence MnIIIMnIV complexes when partial or complete delocalization due to the B parameter is taken into account. These changes depend also on the energy of the relevant intervalence band. Surprisingly, in the two mixed-valence systems studied, the high spin S = 5/2 state lies below S = 7/2. This is consistent with spin coupling between Mn with site spins S1 = 1, S2 =3/2 corresponding to intermediate spin Mn(I) and Mn(II) respectively, instead of the coupling expected from the formal oxidation states, S1 = 2, S2 = 3/2 from high spin Mn(III) and Mn(IV). The spin and charge distributions in the broken symmetry ground states are also consistent with intermediate spin S1 = 1, S2 = 3/2. The calculated charge distributions show strong metal-ligand covalency. In fact, as the formal oxidation states of the Mn sites increase, the net Mn charges generally show a slow decrease, consistent with a very strong ligand → metal charge transfer, particularly from μ-oxo or μ-peroxo ligands. TACN is a better donor ligand than carboxylate, even when calculated on a per donor atom basis. The ligand atom charge transfer order is peroxo ≥ oxo ≫ TACN > acetate. The TACN > acetate ordering is expected from the spectrochemical series, but the strong charge transfer and strong metal - ligand covalency of peroxo and oxo ligands with the Mn sites cannot be simply related to their positions in the spectrochemical series. In the MnIV2(μ-O)2(μ-O2)(TACN) 2, each peroxo oxygen has a small charge (-0.3), much less than found for each μ-O atom (-0.7). The high-spin S = 3 state lies quite low in energy, 8 kcal/mol from our calculations and about 4 kcal/mol based on the experimental Heisenberg spin coupling parameters. Potential molecular oxygen dissociation pathways involving a spin S = 1 state are discussed. Effective ligand field diagrams are constructed from the calculated energy levels which display the competition between spin polarization splitting and the ligand field t2g - eg splitting and allow comparisons of electronic structure among different complexes. The electronic structure and spin coupling of these complexes was also compared to the corresponding "core-only" complexes where both TACN ligands were removed, yielding a far weaker ligand field. There is a strong ferromagnetic shift in the "core-only" complexes compared with the complete TACN complexes, also showing the effects of a weaker ligand field.

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