Relationship of correlation energy and size
M. H. Ang
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorK. Yates
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorI. G. Csizmadia
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorR. Daudel
Centre de Mecanique Ondulatoire Appliquée, Centre National de la Recherche Scientifique, 23 rue du Maroc, Paris XIX, France 75019
Search for more papers by this authorM. H. Ang
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorK. Yates
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorI. G. Csizmadia
Department of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 1A1
Search for more papers by this authorR. Daudel
Centre de Mecanique Ondulatoire Appliquée, Centre National de la Recherche Scientifique, 23 rue du Maroc, Paris XIX, France 75019
Search for more papers by this authorAbstract
Analysis of available data on atoms has led to a relatively simple empirical relationship between the correlation energy and second moment <r2>, a measure of the size of the electron density. With the aid of this simple relationship it is possible to predict correlation energies with fair accuracy given the SCF or Hartree–Fock limit values for the size of the electron density. Preliminary extensions of this work to two- and ten-electron molecules indicate that it may be possible to predict molecular correlation energies to semiquantitative accuracy from SCF data on the electronic distribution.
References
- 1 Modern Theoretical Chemistry, Vols. 3 and 4, H. F. Schaefer, Ed. (Plenum, New York, 1977).
- 2 R.Daudel, P. G.Mezey, J. D.Goddard, and I. G.Csizmadia, Can. J. Chem. 53, 3739 (1975).
- 3 R.Daudel, J. D.Goddard, and I. G.Csizmadia, Int. J. Quantum Chem. 11, 137 (1977).
- 4 R.Daudel, M. E.Stephens, I. G.Csizmadia, C.Kozmutza, E.Kapuy, and J. D.Goddard, Int. J. Quantum Chem. 11, 665 (1977).
- 5 R.Daudel, E.Kapuy, C.Kozmutza, J. D.Goddard, and I. G.Csizmadia, Chem. Phys. Lett. 44, 197 (1976).
- 6 F.Bernardi, I. G.Csizmadia, V. H.Smith, Jr., M. H.Whangbo, and S.Wolfe, Theor. Chim. Acta 37, 171 (1975).
- 7 F.Bernardi, P. G.Mezey, and I. G.Csizmadia, Can. J. Chem. 55, 2417 (1977).
- 8 J. M.McKelvey and A.Streitwieser, J. Am. Chem. Soc. 99, 7121 (1977).
- 9 G. C.Lie and E.Clementi, J. Chem. Phys. 60, 1275 (1975); J. Chem. Phys. 60, 1288 (1975).
- 10 E.Clementi, J. Chem. Phys. 38, 2248 (1963); J. Chem. Phys. 39, 175 (1963).
- 11 M. A.Robb, W. J.Haines, and I. G.Csizmadia, J. Am. Chem. Soc. 95, 42 (1973).
- 12 S.Fraga and G.Malli, Technical Report Nos. TC 6601, TC 6602, and TC 6603, Department of Chemistry, University of Alberta, Edmonton, Alberta (1966); K. M. S.Saxena and S.Fraga, Technical Report No. TC 7201, Department of Chemistry, University of Alberta, Edmonton, Alberta (1972).
- 13 P. O.Löwdin, Adv. Chem. Phys. 2, 207 (1959).
- 14 M. A.Robb, A. C.Roach, J. C.Polanyi, R. E.Kari, and I. G.Csizmadia, J. Chem. Phys. 52, 6205 (1970).
- 15 J. A.Keefer, J. K.SuFu, and R. L.Belford, J. Chem. Phys. 50, 160 (1969).
- 16 J. A.Pople and J. S.Binkley, Mol. Phys. 29, 599 (1975).
- 17 W. C.Ermler and C. W.Kern, J. Chem. Phys. 61, 3860 (1974).
- 18 E.Clementi and H.Popkie, J. Chem. Phys. 57, 4870 (1972).
- 19 R. F.Borkman, J. Chem. Phys. 53, 3153 (1970).
- 20 B. G.Anex, J. Chem. Phys. 38, 1651 (1963).
- 21 L.Salmon and R. D.Poshusta, J. Chem. Phys. 59, 3497 (1973).
- 22 R. N.Porter and G. D.Carney, J. Chem. Phys. 60, 4251 (1974).
- 23 W.Kutzelnigg, R.Ahlrichs, I.Habib-Iskander, and W. A.Bingel, Chem. Phys. Lett. 1, 447 (1967).
- 24 H.Lischka, Theor. Chim. Acta 31, 39 (1973).
- 25 A. W.Weiss, Phys. Rev. A 3, 126 (1971).
- 26 R. E.Kari and I. G.Csizmadia, Theor. Chim. Acta 22, 1 (1971).
- 27 E.Clementi and A.Veillard, J. Chem. Phys. 49, 2415 (1968).
- 28 E.Clementi, J. Chem. Phys. 36, 33 (1962).
- 29 C. F.Bender and E. R.Davidson, Phys. Rev. 183, A23 (1969).
- 30 A. D.McLean and M.Yoshimine, IBM J. Res. Dev. Suppl., (1967).
- 31
H.van Hirschhausen,
D. F.Ilten, and
E.Zeeck,
Chem. Phys. Lett.
40, 80
(1976).
10.1016/0009-2614(76)80124-8 Google Scholar
- 32 M. A.Robb and I. G.Csizmadia, Int. J. Quantum Chem. 5, 605 (1971).
- 33 L. C.Snyder and H.Basch, Molecular Wavefunctions and Properties (Wiley-Interscience, New York, 1972).
