Abstract
Since the advent of photoelectron spectroscopy (Turner et al., 1970; Siegbahn et al., 1971) the interest in atonic and molecular ionization energies has remained very high. At a first approximation the experimental data can be interpreted as a measurement of orbital energies, making therefore a direct connection with orbital theories of electronic structure (Siegbahn and Karlsson, 1982). Notably, in the abinitio framework, the most immediate connection is with the eigenvalues of the Fock operator, through the Koopmans theorem (KT). Within a single determinant approach a refined description may be achieved by reoptimizing orbitals for each final ionic state, the so called ⊿SCF calculation. The energy gained in the ionic states, termed relaxation energy, lowers the calculated IEs, and is particularly important for the deeper hole states, although it may be very significant also in the valence shell, typically in transition metal compounds. It has been soon realized however that important deviations, notably inversions in the ordering of the ionic states, are sometimes obtained both at the KT and ⊿SCF levels. Also additional states become accessible, corresponding to multiple electron excitations, which are forbidden at the KT level, and can be only partly explained by the ⊿SCF approach through the loss of orbital orthogonality.
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Keywords
- Ionization Energy
- Correlation Effect
- Local Density Approximation
- Gradient Correction
- Interelectronic Interaction
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References
Andzelm, J., Winner, E., and Salahub, D. R., 1989, The Challenge of d and f Electrons (Edited by Salahub, D. R., and Zerner, M. C.), p. 228, ACS, Washington, DC.
Baerends, E. J., and Ros, P., 1973, Chem. Phys. 2:52.
Baerends, E. J., and Ros, P., 1975, Mol. Phys. 30:1735.
Baerends, E. J., and Ros, P., 1978, Int. J. Quantum Chen. 12S:169.
Baerends, E. J., Snijders, I. G., de Lange, C. A., and Jonkers, G., 1984, Local Density Approximations in Quantum Chenistry and Solid State Physics (Edited by Dahl, J. P., and Avery, J.), p. 415, Plenum, New York.
Beck, D. R., and Nicolaides, C. A., 1979, Excited States in Quantum Chemistry (Edited by Nicolaides, C. A., and Beck, D. R.), p. 105,329, Reidel, Dordrecht.
Becke, A. D., 1986, J. Chem. Phys. 84:4524.
Bieri, G., Asbrink, L., and von Niessen, W., 1981, J. Electron Spectry. 23:281.
Bohm, M. C., Gleiter, R., and Batich, C. D., 1980, Helv. Chim. Acta 63:990.
Botch, B. H., Dunning, T. H., Jr., and Harrison, J. F., 1981, J. Chem. Phys. 75:3466.
Cade, P. E., Sales, K. D., and Wahl, A. C., 1966, J. Chen. Phys. 44:1973.
Cade, P. E., and Wahl, A. C., 1974, At. Data Nucl. Data Tables 13:339.
Conford, A. B., Frost, D. C., Mc Dowell, C. A., Ragle, I. L., and Stenhouse, F. A., 1971, J. Chem. Phys. 54:2651.
Connolly, J. W. D., and Johnson, K. H., 1971, Chem. Phys. Letters 10:616.
Cook, H., and Karplus, M., 1987, J. Phys. Chem. 91:31.
Coutiere, M. M., Denuynck, J., and Veillard, A., 1972, Theor. Chim. Acta 27:281.
De Alti, G., Decleva, P., and Lisini, A., 1982, Chem. Phys. 66:425.
Decleva, P., De Alti, G., and Lisini, A., 1988, J. Chen. Phys. 89:367.
Decleva, P., Fronzoni, G., and Lisini, A., 1989, Chem. Phys. 134:307.
Decleva, P., Fronzoni, G., De Alti, G., and Lisini, A., 1990, J. Mol. Struct., Theochem, in press.
Decleva, P., and Lisini, A., 1985, Chem. Phys. 97:95.
Decleva, P., and Lisini, A., 1987, Chem. Phys. 112:339.
Demuynck, J., and Veillard, A., 1973, Theor. Chim. Acta 28:241.
Dunlap, B. I., Connolly, J. W. D., and Sabin, J. R., 1979, J. Chem. Phys. 67:3970.
Froese-Fischer, C., 1977, J. Phys. B 10:1241.
Guest, H. F., Hillier, I. H., Mc Dowell, A. A., and Berry, H., 1980, Mol. Phys. 41:519.
Hay, P. J., Dunning, T. H., Jr., and Goddard III, W. A., 1975, J. Chem. Phys. 62:3912.
Hillier, I.H., Guest, H.F., Higginson, B.R., and Lloyd, D.R., 1974, Mol. Phys. 27:215.
Jones, R. O., and Gunnarsson, O., 1989, Rev. Hod. Phys. 61:689.
Katsumata, S., Shiromaru, H., and Kimura, T., 1984, Bull. Chem. Soc. Jpn. 57:1784.
Moncrieff, D., Hi liier, I. H., Saunders, V. R., and von Niessen, W., 1985, Inorg. Chem. 24:4247.
Moore, C. E., 1949, 1952, 1957, Atomic Energy Levels, NBS Circular No 467, Washington, DC.
Perdew, J. P., 1984, Local Density Approximations in Quantum Chemistry and Solid State Physics (Edited by Dahl, J. P., and Avery, J.), p. 173, Plenum, New York.
Plummer, E. W., Loubriel, G., Rajoria, D., Albert, M. R., Seddon, L. G., and Salaneck, W. R., 1980, J. Electron Spectry. 19:35.
Rosch, N., Jorg, H., and Dunlap, B. I., 1986, Quantum Chemistry; the Challenge of Transition Metals and Coordination Chemistry (Edited by Veillard, A.) p. 179, Reidel, Dordrecht.
Salahub, D. R., Lamson, S. H., and Messmer, R. P., 1982, Chem. Phys. Letters 85:430.
Salahub, D. R., Messmer, R. P., and Johnson, K. H., 1976, Mol. Phys. 31:529.
Sambe, H., and Felton, R. H., 1974, J. Chem. Phys. 61:3862.
Schirmer, J., Cederbaum, L. S., and Walter, O., 1983, Phys. Rev. A 28:1237.
Schirmer, J., and Walter, O., 1983, Chem. Phys. 78:201.
Siegbahn, H., and Karlsson, L., 1982, Handbuch der Physik, Vol. 31, (Edited by Melhorn, W.), p. 215, Springer, Berlin.
Siegbahn, K., Nordling, C., Johansson, G., Hedmak, J., Heden, P. F., Hamrin, K., Gelius, U., Bergmark, T., Werme, L. O., Manne, R., and Baer, Y., 1971, ESCA Applied to Free Molecules. North-Holland, Amsterdam.
Sinanoglu, O., 1969, Atomic Physics, Vol. 1 (Edited by Bederson, B., Cohen, V. W., and Pichanik, F. M. S.), p. 131, Plenum, New York.
Slater, J. C., 1972, Adv. Quantum Chem. 6:1.
Smith, S., Hillier, I. H., von Niessen, W., and Guest, M. F., 1989, Chem. Phys. 135:357.
Stoll, H., Golka, E., and Preuss, H., 1980, Theor. Chim. Acta 55:29.
Thunemann, K.-H., Peyerimhoff, S. D., and Buencker, R. J., 1978, J. Mol. Spectry. 70:432.
Tschinke, V., 1989, Thesis, University of Calgary.
Turner, D.W., Baker, C., Baker, A.D., and Brundle, C.R., 1970, Molecular Photoelectron Spectroscopy. Wiley, New York.
Vosko, S.H., Wilk, L., and Nusair, M., 1980, Can. J. Phys. 58:1200.
Wahl, A. C., 1964, J. Chem. Phys. 41:2600.
Wood, J. H., 1980, J. Phys. B: At. Mol. Phys. 13:1.
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Decleva, P., Fronzoni, G., Lisini, A. (1991). Correlation Effects on Ionization Energies. A Comparison of Ab Initio and LDA Results. In: Labanowski, J.K., Andzelm, J.W. (eds) Density Functional Methods in Chemistry. Springer, New York, NY. https://doi.org/10.1007/978-1-4612-3136-3_21
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