The electronic structure and magnetic property of μ-hydroxo bridged manganese porphyrin dimer
The electronic structure and effective exchange integrals (J ab) between two manganese (III) ions of porphyrin dimer (PPMn(III)–OH–Mn(III)PP) were examined by using unrestricted hybrid DFT (UHDFT) methods. The dependence of Jab on bond angle between two manganese (\(\angle\) Mn–OH–Mn) is also calculated to elucidate orbital overlap effect for Jab value in the system. Natural orbital analysis is performed to explain the overlap effect in terms of the instability of the π, σ and δ orbitals by using diradical character.
PACS.31.15.Ar Ab initio calculations 31.15.Ew Density-functional theory
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- Y. Naruta, Seibutu to kinzoku (Kuba pro, Tokyo, 2001), p. 70 (in Japanese) Google Scholar
- J.K. Labanowski, J.W. Andzelm, Density Functional Methods in Chemistry (Springer, New York, 1991) Google Scholar
- R.G. Parr, W. Yang, Density Functional Theory of Atoms and Molecules (Oxford University Press, New York, 1989) Google Scholar
- K. Yamaguchi, M. Okumura, K. Takeda, S. Yamanaka, Int. J. Quant. Chem. 27, 5011 (1993) Google Scholar
- K. Yamaguchi, Y. Takahara, T. Fueno, Appl. Quant. Chem. 155 (1986) Google Scholar
- M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, V.G. Zakrzewski, J.A. Montgomery Jr, R.E. Stratmann, J.C. Burant, S. Dapprich, J.M. Millam, A.D. Daniels, K.N. Kudin, M.C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G.A. Petersson, P.Y. Ayala, Q. Cui, K. Morokuma, D.K. Malick, A.D. Rabuck, K. Raghavachari, J.B. Foresman, J. Cioslowski, J.V. Oritz, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R.L. Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, J.L. Andres, M. Head-Gordon, E.S. Replogle, J.A. Pople, Gaussian 98, Gaussian Inc, Pittsburgh, PA (1998) Google Scholar