The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer
The rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the...
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| Format: | Article |
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MDPI AG
2016-09-01
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| Series: | Inorganics |
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| Online Access: | http://www.mdpi.com/2304-6740/4/4/28 |
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| author | Alessandro Lunghi Federico Totti |
| author_facet | Alessandro Lunghi Federico Totti |
| author_sort | Alessandro Lunghi |
| collection | DOAJ |
| description | The rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of its different terms by electronic structure calculations is expected to steer the rational design of new and more performing SMMs. This paper deals with the ab initio calculation of isotropic and anisotropic exchange contributions in the Fe(III) dimer [Fe 2 (OCH 3 ) 2 (dbm) 4 ]. This system represents the building block of one of the most studied Single Molecule Magnets ([Fe 4 RC(CH 2 O) 3 ) 2 (dpm) 6 ] where R can be an aliphatic chain or a phenyl group just to name the most common functionalization groups) and its relatively reduced size allows the use of a high computational level of theory. Calculations were performed using CASSCF and NEVPT2 approaches on the X-ray geometry as assessment of the computational protocol, which has then be used to evinced the importance of the outer coordination shell nature through organic ligand modelization. Magneto-structural correlations as function of internal degrees of freedom for isotropic and anisotropic exchange contributions are also presented, outlining, for the first time, the extremely rapidly changing nature of the anisotropic exchange coupling. |
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| institution | Directory Open Access Journal |
| issn | 2304-6740 |
| language | English |
| last_indexed | 2024-12-21T18:30:00Z |
| publishDate | 2016-09-01 |
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| series | Inorganics |
| spelling | doaj.art-f2b8a73f72584816a17fda137f6bceed2022-12-21T18:54:18ZengMDPI AGInorganics2304-67402016-09-01442810.3390/inorganics4040028inorganics4040028The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] DimerAlessandro Lunghi0Federico Totti1School of Physics, CRANN and AMBER, Trinity College Dublin, Dublin 2, IrelandDipartimento di Chimica “Ugo Schiff”, Università degli Studi di Firenze, 50019 Sesto Fiorentino, ItalyThe rationalisation of single molecule magnets’ (SMMs) magnetic properties by quantum mechanical approaches represents a major task in the field of the Molecular Magnetism. The fundamental interpretative key of molecular magnetism is the phenomenological Spin Hamiltonian and the understanding of the role of its different terms by electronic structure calculations is expected to steer the rational design of new and more performing SMMs. This paper deals with the ab initio calculation of isotropic and anisotropic exchange contributions in the Fe(III) dimer [Fe 2 (OCH 3 ) 2 (dbm) 4 ]. This system represents the building block of one of the most studied Single Molecule Magnets ([Fe 4 RC(CH 2 O) 3 ) 2 (dpm) 6 ] where R can be an aliphatic chain or a phenyl group just to name the most common functionalization groups) and its relatively reduced size allows the use of a high computational level of theory. Calculations were performed using CASSCF and NEVPT2 approaches on the X-ray geometry as assessment of the computational protocol, which has then be used to evinced the importance of the outer coordination shell nature through organic ligand modelization. Magneto-structural correlations as function of internal degrees of freedom for isotropic and anisotropic exchange contributions are also presented, outlining, for the first time, the extremely rapidly changing nature of the anisotropic exchange coupling.http://www.mdpi.com/2304-6740/4/4/28anisotropic exchangesingle molecule magnetsSpin HamiltonianCASSCFNEVPT2 |
| spellingShingle | Alessandro Lunghi Federico Totti The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer Inorganics anisotropic exchange single molecule magnets Spin Hamiltonian CASSCF NEVPT2 |
| title | The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer |
| title_full | The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer |
| title_fullStr | The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer |
| title_full_unstemmed | The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer |
| title_short | The Role of Anisotropic Exchange in Single Molecule Magnets: A CASSCF/NEVPT2 Study of the Fe4 SMM Building Block [Fe2(OCH3)2(dbm)4] Dimer |
| title_sort | role of anisotropic exchange in single molecule magnets a casscf nevpt2 study of the fe4 smm building block fe2 och3 2 dbm 4 dimer |
| topic | anisotropic exchange single molecule magnets Spin Hamiltonian CASSCF NEVPT2 |
| url | http://www.mdpi.com/2304-6740/4/4/28 |
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