Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
Search:
   
 
 
 
Previous Article
Relationships between electric field shielding tensors and infrared or Raman intensities: An explanation based on nonlocal polarizability densities
New equations for the derivatives of molecular dipole moments and polarizabilities with respect to nuclear coordinates are derived in terms of nonlocal polarizability densities, linear and nonlinear. ...
Next Article
Energies and electric dipole moments of the low lying electronic states of the alkaline earth monohalides from an electrostatic polarization model
A simple electrostatic polarization model is applied to the low lying electronic states A 2 , B 2 +, and A 2 of the alkaline earth monohalides which correlate to the electronic d state of the free me...

A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions

J. Chem. Phys. 90, 4916 (1989); doi:10.1063/1.456588

Issue Date: 1 May 1989

You are not logged in to this journal. Log in

János Pipek and Paul G. Mezey
Department of Chemistry and Department of Mathematics, University of Saskatchewan, Saskatoon, Saskatchewan, S7N 0W0 Canada
A new intrinsic localization algorithm is suggested based on a recently developed mathematical measure of localization. No external criteria are used to define a priori bonds, lone pairs, and core orbitals. It is shown that the method similarly to Edmiston–Ruedenberg's localization prefers the well established chemical concept of sigma–pi separation, while on the other hand, works as economically as Boys' procedure. For the application of the new localization algorithm, no additional quantities are to be calculated, the knowledge of atomic overlap intergrals is sufficient. This feature allows a unique formulation of the theory, adaptable for both ab initio and semiempirical methods, even in those cases where the exact form of the atomic basis functions is not defined (like in the EHT and PPP calculations). The implementation of the procedure in already existing program systems is particularly easy. For illustrative examples, we compare the Edmiston–Ruedenberg and Boys localized orbitals with those calculated by the method suggested here, within both the CNDO/2 and ab initio frameworks (using STO-3G and 6-31G** basis sets) for several molecules (CO, H2CO, B2H6, and N2O4). Some similarities concerning the localization procedures of von Niessen as well as Magnasco and Perico are also discussed. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 21 October 1988; accepted 12 January 1989
Permalink: http://link.aip.org/link/?JCPSA6/90/4916/1
BUY THIS ARTICLE   (US$24)
Download PDF (1317 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 31.20.Ej
    Electronic structure of atoms and molecules: theory Specific calculations and results Ab initio MO calculations
  • YEAR: 1988-89

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (46)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. S. F. Boys, Rev. Mod. Phys. 32, 296 (1960).
  2. J. M. Foster and S. F. Boys, Rev. Mod. Phys. 32, 300 (1960).
  3. S. F. Boys, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P.-O. Löwdin (Academic, New York, 1966), p. 253.
  4. C. Edmiston and K. Ruedenberg, Rev. Mod. Phys. 35, 457 (1963).
  5. C. Edmiston and K. Ruedenberg, J. Chem. Phys. 43, S97 (1965).
  6. C. Edmiston and K. Ruedenberg, in Quantum Theory of Atoms, Molecules and the Solid State, edited by P.-O. Löwdin (Academic, New York, 1966), p. 263.
  7. W. von Niessen, J. Chem. Phys. 56, 4290 (1972).
  8. D. A. Kleier, T. A. Halgren, J. H. Hall, Jr., and W. N. Lipscomb, J. Chem. Phys. 61, 3905 (1974).
  9. J. Cizek, W. Förner, and J. Ladik, Theoret. Chim. Acta 64, 107 (1983).
  10. V. Magnasco and A. Perico, J. Chem. Phys. 47, 971 (1967).
  11. K. Ruedenberg, in Modern Quantum Chemistry, edited by O. Sinanoglu (Academic, New York, 1965), Vol. 1, p. 85.
  12. M. C. Böhm, Theoret. Chim. Acta 59, 609 (1981).
  13. B. J. Duke, J. Mol. Struct. (Theochem) 152, 319 (1987).
  14. A. E. Reed and F. Weinhold, J. Chem. Phys. 83, 1736 (1985).
  15. M. Rajzmann, B. Brenier, and K. F. Purcell, Theor. Chim. Acta 72, 13 (1987).
  16. E. Kapuy, Z. Csépes, and C. Kozmutza, Intern. J. Quantum Chem. 23, 981 (1983).
  17. E. Kapuy, Z. Csépes, and J. Pipek, Acta Phys. Hung. 55, 365 (1984).
  18. J. Pipek and J. Ladik, Chem. Phys. 102, 445 (1986).
  19. W. Förner, J. Cizek, P. Otto, J. Ladik, and O. E. Steinborn, Chem. Phys. 97, 235 (1985).
  20. W. Förner, J. Ladik, P. Otto, and J. Cizek, Chem. Phys. 97, 251 (1985).
  21. W. Förner, Chem. Phys. 114, 21 (1987).
  22. J. J. Kaufman, Intern. J. Quantum Chem. 31, 179 (1987).
  23. J. Pipek, Chem. Phys. Lett. 111, 430 (1984).
  24. J. Pipek, Chem. Phys. Lett. 143, 293 (1988).
  25. R. Barr and H. Basch, Chem. Phys. Lett. 32, 537 (1975).
  26. R. C. Haddon and G. R. J. Williams, Chem. Phys. Lett. 42, 453 (1976).
  27. J. M. Leonard and W. L. Luken, Theoret. Chim. Acta 62, 107 (1982).
  28. J. M. Leonard and W. L. Luken, Intern. J. Quantum Chem. 25, 355 (1984).
  29. R. Kari, Intern. J. Quantum Chem. 25, 321 (1984).
  30. T. Sano, S. Narita, and Y. J. l'Haya, Chem. Phys. Lett. 138, 291 (1987).
  31. P. G. Mezey, Intern. J. Quantum Chem., Quant. Biol. Symp. 12, 113 (1986).
  32. P. G. Mezey, J. Comput. Chem. 8, 462 (1987).
  33. P. G. Mezey, Intern. J. Quantum Chem., Quant. Biol. Symp. 14, 127 (1987).
  34. G. A. Arteca and P. G. Mezey, Intern. J. Quantum Chem., Quant. Biol. Symp. 14, 133 (1987).
  35. G. A. Arteca, V. B. Jammal, P. G. Mezey, J. S. Yadav, M. A. Hermsmeier, and T. M. Gund, J. Molec. Graphics 6, 45 (1988).
  36. G. A. Arteca, V. B. Jammal, and P. G. Mezey, J. Comput. Chem. 9, 608 (1988).
  37. D. Caldwell and H. Eyring, in Advances in Quantum Chemistry, edited by P.-O. Löwdin (Academic, New York, 1978), Vol. 2, p. 93.
  38. W. L. Luken and D. N. Beratan, Theoret. Chim. Acta 61, 265 (1982).
  39. J. Pipek (submitted for publication).
  40. I. Mayer, Chem. Phys. Lett. 97, 270 (1983).
  41. J. Pipek, Intern. J. Quantum Chem. 27, 527 (1985).
  42. R. S. Mulliken, J. Chem. Phys. 23, 1833 (1955).
  43. R. S. Mulliken, J. Chem. Phys. 23, 1841 (1955).
  44. J. Pipek and P. G. Mezey, Intern. J. Quantum Chem. Quantum Chem. Symp. 22, 1 (1988).
  45. P. G. Perkins and J. P. Stewart, J. Chem. Soc. Faraday Trans. 2 78, 285 (1982).
  46. E. Switkes, R. M. Stevens, W. N. Lipscomb, and M. D. Newton, J. Chem. Phys. 51, 2085 (1969).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics