A New Look at Electron Localization†
Corresponding Author
Dr. A. Savin
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)Search for more papers by this authorProf. Dr. A. D. Becke
Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6 (Canada)
Search for more papers by this authorDr. J. Flad
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. R. Nesper
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. H. Preuss
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. H. G. von Schnering
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorCorresponding Author
Dr. A. Savin
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)Search for more papers by this authorProf. Dr. A. D. Becke
Department of Chemistry, Queen's University, Kingston, Ontario K7L 3N6 (Canada)
Search for more papers by this authorDr. J. Flad
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. R. Nesper
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. H. Preuss
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorProf. Dr. H. G. von Schnering
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, W-7000 Stuttgart 80 (FRG)
Search for more papers by this authorThis work was supported by the Fonds der Chemischen Industrie, the Deutsche Forschungsgemeinschaft, the Höchst AG (Frankfurt), the Bundesministerium für Forschung und Technologie and the Natural Sciences and Engineering Research Council of Canada. We thank F.-X. Fraschio, M. Kohout and B. Miehlich (Universität Stuttgart) for the assistance with the computer graphics. We are indebted to Prof. P. Fulde (Stuttgart) and Prof. W. H. E. Schwarz (Siegen) for valuable suggestions.
Graphical Abstract
Bonds and lone electron pairs can be made “visible” when the electron density distribution is used to calculate the electron localization function (ELF). This paper presents a computer-graphics image of ELF in colors which represent the extent of the localization (at the right a black-and-white picture of N2).
References
- 1 W. England, L. S. Salmon, K. Ruedenberg, Top. Curr. Chem. 23 (1971) 31.
- 2 W. England, Int. J. Quantum Chem. 5 (1971) 683.
- 3 A. D. Becke, K. E. Edgecombe, J. Chem. Phys. 92 (1990) 5397.
- 4 J. E. Lennard-Jones, J. Chem. Phys. 20 (1952) 1024.
- 5 R. J. Gillespie, R. S. Nyholm, Q. Rev. 11 (1957) 339.
- 6(a)
Details of the calculations: Basis sets:
W. J. Hehre,
R. Ditchfield,
J. A. Pople,
J. Chem. Phys.
56
(1972) 2257;
P. C. Hariharan,
J. A. Pople,
Theor. Chim. Acta
28
(1973) 213;
M. F. Frankl,
W. J. Pietro,
W. J. Hehre,
J. S. Binkley,
M. S. Gordon,
D. J. Defrees,
J. A. Pople,
J. Chem. Phys.
77
(1982) 3654 (for 6–11, ClF),
G. Igel-Mann,
C. Feller,
H.-J. Flad,
A. Savin,
H. Stoll,
H. Preuss,
Mol. Phys.
68
(1989) 209 (for the Sn compounds);
F. B. van Duijneveldt,
IBM Res. Rep.
945
(1991) (contracted after
G. C. Lie,
E. Clementi,
J. Chem. Phys.
60
(1974) 1275) (for all other compounds);
(b)
Molecular Structures:
K. P. Huber,
G. Herzberg:
Molecular Spectra and Molecular Structures,
Vol. 4,
Van Nostrand, New York
1979 (diatomic molecules);
10.1007/978-1-4757-0961-2 Google ScholarL. E. Sutton (ed.): Tabies of Interatomic Distances and Configurations in Molecules and Ions, The Chemical Society, London 1958 (5–9 and FHF⊖); I. Boustani, W. Pewestorf, P. Fantucci, V. Bonačić-Koutecký, J. Koutecký, Phys. Rev. B 25 (1987) 9437 (Li cluster); G. Igel-Mann, G. Igel-Mann C. Feller, H.-J. Flad, A. Savin, H. Stoll, H. Preuss, Mol. Phys. 68 (1989) 209 (SnO); G. Igel-Mann, C. Feller, H. Preuss, J. Mol. Struct. (THEOCHEM) 209 (1990) 313 (Sn2O2);10.1016/0166-1280(90)80085-3 Google ScholarG. Trinquier, J. P. Malrieu, P. Riviere, J. Am. Chem. Soc. 104 (1982) 4529 (18); W. Plass, A. Savin, H. Stoll, H. Preuss, R. Nesper, H. G. von Schnering, Inorg. Chem. 29 (1990) 260 (Cu4Sn4); (c) SCF program: L. E. McMurchie, S. T. Elbert, S. R. Langhoff, E. R. Davidson: Program MELD, NRCC program QC04 (graciously supplied by Prof. Dr. E. R. Davidson); W. Meyer, P. Pulay, E. A. Reinsch, H. J. Werner: Program MOLPRO (graciously supplied by Prof. H. J. Werner); both programs were installed on the Cray-2 of the Computer Center of the Universität Stuttgart by Prof. H. Stoll, Dr. U. Wndig and B. Miehlich.
- 7 G. Igel-Mann, H. Stoll, H. Preuss, Mol. Phys. 65 (1988) 1321.
- 8 W. C. Clinton, J. Nakhleh, F. Wunderlich, Phys. Rev. 177 (1969) 1; W. C. Clinton, A. J. Galli, L. J. Massa, Phys. Rev. 177 (1969) 7; W. C. Clinton, G. A. Henderson, J. V. Prestia, Phys. Rev. 177 (1969) 13; W. C. Clinton, G. B. Lamers, Phys. Rev. 177 (1969) 19; W. C. Clinton, A. J. Galli, G. A. Henderson, G. B. Lamers, L. J. Massa, J. Zarur, Phys. Rev. 177 (1969) 27; W. C. Clinton, L. J. Massa, Phys. Rev. Lett. 29 (1972) 1363; R. F. Stewart, J. Chem. Phys. 51 (1969) 4569.
- 9 P. Coppens, T. V. Willoughby, L. N. Gonka, Acta Crystallogr. Sect. A 27 (1971) 248; W. H. E. Schwarz, B. Müller, Chem. Phys. Lett. 166 (1990) 621.
- 10 H. Schmider, V. H. Smith, Jr., W. Weyrich, Trans. Am. Crystallogr. Assoc. 24 (1991), in press.
- 11 J. Flad, F.-X. Fraschio, B. Miehlich: Program GRAPA, Institut für Theoretische Chemie der Universität Stuttgart, 1989.
- 12 H. E. White, Phys. Rev. 37 (1931) 1416.
- 13 W. Kutzelnigg: Einführung in der Theoretische Chemie, Vol. 2, Verlag Chemie, Weinheim, 375.
- 14 Compare D. E. Goldberg, P. B. Hitchock, M. F. Lappert, K. M. Thomas, A. J. Thomas, T. Fjeldberg, A. Haaland, B. E. R. Schilling, J. Chem. Soc. Dalton Trans. 1986, 2387.
