Abstract
Zeolite chemistry has developed into one of the most fascinating, and in many cases most structurally defined, fields of interface science. Its appeal in both fundamental and applied surface science, including that of intracavital complexes and clusters involved in separation processes and catalysis, has been documented by thousands of papers in the open literature as well as the body of patented literature. The theoretical methodology also has advanced to a level, still rapidly developing, where relatively large systems, including periodic systems, can be handled by all-electron calculations from the first principles. It is now possible to optimize geometries of zeolites with different cations and framework substituents and to predict their structural and electronic properties.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Klier, K. (1988) Transition-metal ions in zeolites: The perfect surface sites, Langmuir 4, 13–25.
Klier, K., Kellerman, R., and Hutta, P.J. (1974) Spectra of synthetic zeolites containing transition metal ions-V. II-Complexes of olefins and acetylene with Co(II)A molecular sieve, J. Chem. Phys. 61, 4224–4234.
George, P. and McClure, D.S. (1959) in F.A. Cotton (ed.), Progress in Inorganic Chemistry, Interscience Publishers, New York and London, 1, p. 381.
An early review of LFT approaches to zeolite science by Kellerman, R. and Klier, K. (1978) “Intrazeolitic transition-metal ion complexes” appeared in M.W. Roberts and J.M. Thomas (eds), Surface and Defect Properties in Solids, Chemical Society London, 4, pp. 1–33.
Sugano, S., Tanabe, Y., and Kamimura, H. (1970) Multiplets of Transition-Metal Ions in Crystals, Academic Press, New York and London.
Klier, K., and Rálek, M. (1968) Spectra of synthetic zeolites containing transition metal ions — II. Ni+2 ions in Type A Linde molecular sieves, J. Phys. Chem. Solids 29, 951–957.
Klier, K., Hutta, P.J., and Kellerman, R. (1977) Electronic structure and stability of transition metal ions in zeolites, in J.S. Kratzer (ed.) ACS Symposium Series, American Chemical Society, Washington, pp. 108–119; the earliest demonstration of the approach in zeolite science is by Polák, P., and ern I, V. (1968) Spectra of synthetic zeolites containing transition metal ions-I. Theory of the d9(d1) and d8(d2) electronic configuration in the crystal field of D3h symmetry, J. Phys. Chem. Solids 29, 945-950; and by Polák, P., and Klier, K. (1969) Spectra of synthetic zeolites containing transition metal ions — III. A simple model calculation of the system adsorbed molecule-NiA zeolite, J. Phys. Chem. Solids 30, 2231-2233.
The pioneering work by the leading physicists since the landmark paper by Bethe, H. (1929) Termaufspaltung in Kristallen, Ann. Physik 3, 133, is cited and analyzed in J.S. Griffith (ed.), The Theory of Transition-Metal Ions, Cambridge Univ. Press, Cambridge, U.K. (1964). Subsequent work and many publications focused more on molecular orbital theory, as in Cotton, F.A. (1990) Chemical Applications of Group Theory (3rd ed.), Wiley & Sons, New York/Chichester/Brisbane/Toronto/Singapore.
A seminal paper dealing with dynamical Jahn-Teller effect by Toyozawa, Y. and Inoue, M. (1966) Dynamical Jahn-Teller effect in alkali halide phosphors containing heavy metal ions, J. Phys. Soc. Japan 21, 1663 stimulated the author’s treatment of this phenomenon in zeolites, cf. ref. [1].
Extensive treatment of magnetic phenomena studied by paramagnetic resonance is in Abragam, A. and Bleaney, B. (1970) Electron Paramagnetic Resonance of Transition Ions, Dover Publications, New York.
Verberckmoes, A.A., Schoonheydt, R.A., Ceulemans, A., Delabie, A., and Pierloot, K. (1998) Semiempirical and ab initio calculations of the spectroscopic properties of Co(II) coordinated to six-rings in zeolites, Proc. 12 th Int. Zeolite Conf I, Materials Research Soc., Warrendale, PA, pp. 387–400.
Perdew, J.P., Burke, K., and Ernzerhof, M. (1996) Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865.
A lucid monograph by Parr, R.G., and Yang, W. (1989) Density-Functional Theory of Atoms and Molecules: Intro. Ser. of Monographs on Chemistry-16, Oxford Sci. Press, New York; Clarendon Press, Oxford, covers the foundations of DFT as well as chemical applications. The landmark papers are by Hohenberg, P. and Kohn, W. (1964) Inhomogeneous electron gas, Phys. Rev. 136, B864 and by Kohn, W., and Sham, L.J. (1965) Self-consistent equations including exchange and correlation effects, Phys. Rev. 140, A1133.
Stowasser, R., and Hoffmann, R. (1999) What do the Kohn-Sham orbitals and eigenvalues mean?, J. Am. Chem. Soc. 121, 3414–3420.
Bridgeman, A.J. and Rothery, J. (2000) Periodic trends in the diatomic monoxides and monosulfides of the 3d transition series, Dalton Trans., J. Chem. Soc. 211.
Kittel, C. (1986) Introduction to Solid State Physics, Wiley & Sons (6th ed.), New York/Chichester/Brisbane/Toronto/Singapore, p. 104.
Singh, D.J. (1994) Pseudopotentials and the LAP W Method, Kluwer Academic Publishers, Dordrecht.
Blaha, P., Schwarz, K., and Luitz, J. (1999) WIEN97, A Full Potential Linearized Augmented Plane Wave Package for Calculating Crystal Properties, Karlheinz Schwarz, Techn. Universität Wien, Austria. ISBN 3-9501031-0.
Novák, P., Harmon, B.F., Persson, C., Blaha, P., Diviš, M, Eshrig, H., and Richter, M. (1999) Implementation of the spin-orbit coupling into the Wien97, P. Novák’s Lecture Notes, Users Guide for ref. [18].
Klier, K., Wichterlová, and Dědeček, J. (1999) Coordination and electronic structure of extraframework transition metal-ions by High-Resolution X-Ray Photoelectron and Optical Spectroscopy, in M.M.J. Treacy, B.K. Marcus, M.E. Bisher & J.B. Higgins (eds), Proc. 12 th Int. Zeolite Conference, Materials Research Society, Warrendale, PA, pp. 401–408.
Hush, N.S. and Pryce, M.H.L. (1958) Influence of the crystal-field potential on interionic separation in salts of divalent iron-group ions, J. Chem. Phys. 28, 244.
Penney, W.G. (1940) A note on the bonding powers of groups of d electrons, Trans. Faraday Soc., 35, 627. Here the concept of crystal-field stabilization energy (CFSE), or ligand-field stabilization energy (LFSE) explaining the “double-hump” pattern of heats of formation of hexahydrates of transition metal ions was introduced for the first time.
Klier, K., Ma, Q., Alamgir, F., Glueckstein, J., Finney, S., Streater, A., Tyler, M., Zeszotarski, J., Lehigh University course Chem 494, Quantum Chemistry, Fall 1999, Bethlehem, PA, USA.
Bagus, M.D., Reed, T.B., and Strauss, A.J. (1972) Electrical and magnetic properties of TiO and VO, Phys. Rev. B, 5, 2775; Denker, S.P. (1968) Electronic properties of titanium, J. Appl. Phys. 37, 142.
Analysis in Ref. [3], Table V gives thermodynamic splitting parameters (Dq) for Ti(II) and V(II) which seem to imply high-spin configurations, but those for TiO and VO are not given.
To be published as separate reports for each oxide.
Experimental VB XPS spectra of Cu(I)Na FAU and Co(II) LTA are given in Figs. 1 and 3 of Ref. [20], respectively.
Hunsicker, R.A., and Klier, K. (2000) Spectral analysis and DFT computations of zeolitic materials (Abstract 241), COLLOID 2000: 74th ACS Colloid and Surface Science Symposium, June 19-21, 2000, Lehigh University, Bethlehem, PA, USA.
Hess, J.S. (1998) Fundamental interactions at selected catalyst surfaces: methane/palladium, oxygen/palladium, and cesium/molybdenum disulfide. Dissertation, Lehigh University, Bethlehem, PA, USA.
Johansson, M., and Klier, K. (1997) Surface acidity (Brønsted and Lewis) by high resolution X-ray photoelectron spectroscopy, Topics in Catalysis 4, 99.
Yanagida, R.Y., Vance, T.B., and Seff, K. (1974) Five-coordinate and three-coordinate manganese(II). Hydrated and dehydrated crystal structures of partially manganese(II)-exchanged zeolite A, Inorg. Chem. 13, 723.
Kellerman, R., Hutta, P.J., and Klier, K. (1974) J. Am. Chem. Soc., 96, 5946.
Peterson, B., private communication. The GULP code is based on the work of Lewis, G.V., and Catlow, C.R.A. (1985) Potential models for ionic oxides, J. Phys. C 18, 1149–1161.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2001 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Klier, K. (2001). Electronic Structure of Transition-Metal Ion Containing Zeolites. In: Centi, G., Wichterlová, B., Bell, A.T. (eds) Catalysis by Unique Metal Ion Structures in Solid Matrices. NATO Science Series, vol 13. Springer, Dordrecht. https://doi.org/10.1007/978-94-010-0782-5_8
Download citation
DOI: https://doi.org/10.1007/978-94-010-0782-5_8
Publisher Name: Springer, Dordrecht
Print ISBN: 978-0-7923-6875-5
Online ISBN: 978-94-010-0782-5
eBook Packages: Springer Book Archive