The mapping of the local contributions of Fermi and Coulomb correlation into intracule and extracule density distributions

Journal of Chemical Physics

Volumn 113, Issue 7, 2000, Pages 2530-2543

  Fradera, Xavier ^a   Duran, Miquel ^a   Mestres, Jordi ^b  

^a UNIVERSITY OF GIRONA   (Spain)

^b NV ORGANON   (Netherlands)

Author keywords

[No Author keywords available]

Indexed keywords

ARGON; CARBON INORGANIC COMPOUNDS; CARRIER CONCENTRATION; CORRELATION METHODS; FERMI LEVEL; HELIUM; LAPLACE TRANSFORMS; NEON; TOPOLOGY;

FERMI-COULOMB CORRELATIONS; HARTREE-FOCK THEORY; INTRACULE-EXTRACULE DENSITY DISTRIBUTIONS;

MOLECULAR PHYSICS;

EID: 0034249015     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (44)

1. R. F. W. Bader, Atoms in Molecules: A Quantum Theory (Clarendon, Oxford, 1990).
2. E. R. Davidson, Reduced Density Matrices in Quantum Chemistry (Academic, New York, 1976).
3. A. J. Coleman, Int. J. Quantum Chem. 18, 457 (1967).
4. A. J. Thakkar and V. H. Smith, Jr., Chem. Phys. Lett. 42, 476 (1976).
5. A. E. Carlsson and N. W. Ashcroft, Phys. Rev. B 25, 3474 (1982);
6. A. J. Thakkar, J. Chem. Phys. 84, 6830 (1986).
7. E. Valderrama, J. M. Ugalde, and R. J. Boyd, in Advances in the Theory of Many-Electron Densities and Reduced Density Matrices, edited by J. Cioslowski (Kluwer Academic/Plenum, New York, in press).
8. A. J. Thakkar and N. J. Moore, Int. J. Quantum Chem., Symp. 15, 393 (1981).
9. A. J. Thakkar, A. N. Tripathi, and V. H. Smith, Int. J. Quantum Chem. 26, 157 (1984).
10. C. Sarasola, J. M. Ugalde, and R. J. Boyd, J. Phys. B 23, 1095 (1990).
11. C. A. Coulson and A. H. Neilson, Proc. Phys. Soc. London 78, 831 (1961).
12. R. J. Boyd and C. A. Coulson, J. Phys. B 7, 1805 (1974).
13. J. Cioslowski and G. Liu, J. Chem. Phys. 105, 8187 (1996).
14. X. Fradera, M. Duran, and J. Mestres, J. Chem. Phys. 107, 3576 (1997).
15. X. Fradera, M. Duran, and J. Mestres, Can. J. Chem. 78, 328 (2000).
16. J. Cioslowski and G. Liu, J. Chem. Phys. 109, 8225 (1998);
17. J. Cioslowski and G. Liu, J. Chem. Phys. ibid. 110, 1882 (1999);
18. J. Cioslowski, G. Liu, J. Rychlewski, W. Cencek, and J. Komasa, J. Chem. Phys. ibid. 111, 3401 (1999).
19. X. Fradera, C. Sarasola, J. M. Ugalde, and R. J. Boyd, Chem. Phys. Lett. 304, 393 (1999).
20. R. McWeeney, Methods of Molecular Quantum Mechanics (Academic, London, 1969).
21. R. F. W. Bader, A. Streitwieser, A. Neuhaus, K. E. Laidig, and P. Speers, J. Am. Chem. Soc. 118, 4959 (1996);
22. R. F. W. Bader, S. Johnson, and T.-H. Tang, J. Phys. Chem. 100, 15398 (1996);
23. R. J. Gillespie, D. Bayles, J. Platts, G. L. Heard, and R. F. W. Bader, J. Phys. Chem. A 102, 3407 (1998);
24. R. F. W. Bader, and G. L. Heard, J. Chem. Phys. 111, 8789 (1999).
25. X. Fradera, M. A. Austen, and R. F. W. Bader, J. Phys. Chem. A 103, 304 (1999).
26. X. Fradera, M. Duran, and J. Mestres, J. Comput. Chem. (in press).
27. A. M. Lee and P. M. W. Gill, Chem. Phys. Lett. 313, 271 (1999).
28. M. W. Schmidt et al., J. Comput. Chem. 14, 1347 (1993).
29. J. Cioslowski and G. Liu, J. Chem. Phys. 105, 4151 (1996).
30. 2E(R) distributions and its components was carried out by using a gradient minimization procedure. Nuclear geometries were used to generate a suitable starting point for each of the formal electron-electron interactions. An exhaustive search of all the local minima possible in the different intracule and extracule distributions was not attempted.
31. T. Koga and H. Matsuyama, J. Chem. Phys. 107, 10062 (1997).
32. T. Koga and H. Matsuyama, J. Phys. B 30, 5631 (1997).
33. F. Arias de Saavedra, I. Porras, E. Buendía, and F. J. Gálvez, J. Phys. B 28, 3123 (1995).
34. A. Sarsa, F. J. Gálvez, and E. Buendía, J. Chem. Phys. 109, 7075 (1998).
35. F. J. Gálvez, E. Buendía, and A. Sarsa, J. Chem. Phys. 111, 3319 (1999).
36. J. M. Mercero, J. E. Fowler, C. Sarasola, and J. M. Ugalde, Phys. Rev. A 59, 4255 (1999).
37. However, by using different post-HF wave functions, different conclusions are reached in Refs. 29 and 30 on the effect of electron correlation on atomic counterbalance densities. The same post-HF methodology of Ref. 30 (CI) is used in the present paper, and similar results are obtained for the counterbalance densities.
38. R. P. Sagar, A. C. T. Ku, and V. H. Smith, Jr., J. Chem. Phys. 88, 4367 (1988).
39. Z. Shi and R. J. Boyd, J. Chem. Phys. 88, 4375 (1988).
40. C. Sarasola, L. Domínguez, M. Aguado, and J. M. Ugalde, J. Chem. Phys. 96, 6778 (1992).
41. X. Fradera, M. Duran, and J. Mestres, Theor. Chem. Acc. 99, 44 (1998).
42. J. M. Ugalde and C. Sarasola, Phys. Rev. A 49, 3081 (1994).
43. M. Solà, J. Mestres, J. M. Oliva, M. Duran, and R. Carbó, Int. J. Quantum Chem. 58, 361 (1996).
44. At post-HF levels of theory it is generally found that I(0) is smaller than 〈ρ〉/4, even though a formal proof of this inequality has not been derived yet. See X. Fradera, M. Duran, E. Valderrama, and J. M. Ugalde, Phys. Rev. A (in press).