Hostname: page-component-cd9895bd7-jn8rn Total loading time: 0 Render date: 2024-12-27T01:52:40.294Z Has data issue: false hasContentIssue false
  • English
  • Français

High Spin Mn Molecular Clusters: Spin State Effects On the Outer Core-Level Multiplet Structures

Published online by Cambridge University Press:  17 March 2011

A. J. Nelson ,
J. G. Reynolds  and
George Christou
A. J. Nelson
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
J. G. Reynolds
Affiliation:
Lawrence Livermore National Laboratory, Livermore, CA 94550
George Christou
Affiliation:
Indiana University, Department of Chemistry, Bloomington, IN 47405
Get access

Abstract

Oxo-bridged manganese polynuclear complexes have applications in a variety of technologies, such as single-molecule nanomagnets, catalysis and photosynthetic redox chemistry. The reason that these types of compounds are capable of such important and varied technologies is thought to be because they possess ground states with large spin values. However, the electronic, structural and magnetochemical relationships are not well understood and need to be thoroughly investigated to adequately explain why Mn is such an integral part of so many useful processes. X-ray photoemission spectroscopy was used to study the Mn 3p, 3s and valence band electronic behavior as a function of Mn cluster structural properties, where the cluster size and nuclearity are systematically varied. Results show a chemical shift of the Mn 3p3/2,1/2 spin-orbit pair related to the cluster size and nuclearity. Also, the Mn 3s 7S and 5S final state multiplet components shift since they involve the binding energy of a ligand valence electron. In addition, the branching ratio of the 7S:5S states is related to the 3s–3d electron correlation. Specifically, in the 7S state, the remaining 3s electron is well correlated with 3d electrons of parallel spin, while in the 5S state the two spins are antiparallel. Changes in this electron correlation are clearly observed in the 7S:5S branching ratio as a function of cluster size and ligand electronegativity.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 635: Symposium C – Anisotropic Nanoparticles-Synthesis, Characterization & Applications , 2001 , C4.13
Copyright
Copyright © Materials Research Society 2001

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Yachandra, V.K., Sauer, K., and Klein, M.P., Chem. Rev. 96, 2927 (1996).Google Scholar
2. Groves, J.T. and Stern, M.K., J. Am. Chem. Soc. 110, 8628 (1988).Google Scholar
3. Groves, J.T., Lee, J., and Marla, S.S., J. Am. Chem. Soc. 119, 6269 (1997).Google Scholar
4. Limburg, J., Brudvig, G.W., and Crabtree, R.H., J. Am. Chem. Soc. 119, 2761 (1997).Google Scholar
5. Ruiz-Molina, D., Christou, G., Hendrickson, D.N., Mol. Cryst. Liq. Cryst. 343, 335 (2000).Google Scholar
6. Yoo, J., Brechin, E.K., Yamaguchi, A., Nakano, M., Huffman, J.C., Maniero, A.L., Brunel, L.C., Awaga, K., Ishimoto, H., Christou, G., and Hendrickson, D.N., Inorg. Chem. 39, 3615 (2000).Google Scholar
7. Bagus, P.S., Freeman, A.J. and Sasaki, F., Phys. Rev. Lett. 30, 850 (1973).Google Scholar
8. Fadley, C.S., in Electron Spectroscopy: Theory, Techniques, and Applications, edited by Brundle, C.R. and Baker, A.D. (Academic, London, 1978) Vol. II, Chap. 1.Google Scholar
9. Hermsmeier, B., Fadley, C.S., Sinkovic, B., Krause, M.O., J. Jimenez-Mier, Gerard, P., Carlson, T.A., Manson, S.T. and Bhattacharya, S.K., Phys. Rev. B48, 12425 (1993).Google Scholar
10. Fujiwara, M., Matsushita, T. and Ikeda, S., J. Electron Spectroscopy Rel. Phenom. 74, 201 (1995).Google Scholar
11. Nelson, A. J., Reynolds, J. G. and Roos, J. W., J. Vac. Sci. Technol. A18(4), 1072 (2000).Google Scholar
12. Wemple, Michael W., Tsai, H.-L., Wang, S., Cluade, Juan Pablo, Streib, W.E., Huffman, J.C., Hendrikson, D.N. and Christou, George, Inorg. Chem. 35, 6437 (1996).Google Scholar
13. Wang, S., Tsai, H.-L., Libby, Eduardo, Folting, K., Streib, W.E., Hendrikson, D.N. and Christou, George, Inorg. Chem. 35, 7578 (1996).Google Scholar
14. Wang, Sheyi, Wemple, Michael S., Yoo, Jae, Folting, Kirsten, Huffman, John C., Hagen, Karl S., Hendrickson, David N., and Christou, George, Inorg. Chem. 39, 1501 (2000).Google Scholar