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Abstract:

It is well known that the reduced density operator of order q is the essential tool for describing the electronic distribution in many-electron extended systems such as crystalline and molecular systems. In the present work this operator was used to generate a rigorous and general model of population analysis for particles (q=1), "pairons" (q=2), or in a more general sense, q-ons. For all q, it is possible to define population analyses of linear and non-linear structures, with regard to the mathematical shape of the generating functional of the particular analysis. If q=1, one of the linear types of analysis is the Mulliken type which is derived from a different basis from the original derivation, and from the non-linear type the Armstrong, Perkins and Stewart type (APS ) may be derived rigorously from physical principles, thereby allowing generalization of these definitions to more sophisticated wavefunctions. We define, as a byproduct, the bond multiplicity or degree of bonding, and the active, inactive and gross or proper populations in atoms within this last type of analysis which we call the statistical population analysis (SPA), in order to make explicit its nature. Furthermore, we apply SPA to the SCF closed shell formalism for first-order (q=1) and second-order (q=2) distributions. The numerical results are presented. © 1991.

Registro:

Documento: Artículo
Título:Quantum statistical nature of the chemical bond. Part I. Theoretical framework of population analysis and application to SCF closed shell wavefunctions
Autor:Bochicchio, R.C.
Filiación:Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. I, 1428 Buenos Aires, Argentina
Año:1991
Volumen:228
Número:C
Página de inicio:209
Página de fin:225
DOI: http://dx.doi.org/10.1016/0166-1280(91)90058-R
Título revista:Journal of Molecular Structure: THEOCHEM
Título revista abreviado:J. Mol. Struct. THEOCHEM
ISSN:01661280
CODEN:THEOD
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_01661280_v228_nC_p209_Bochicchio

Referencias:

  • Mulliken, (1955) J. Chem. Phys., 23, p. 1833
  • Mulliken, (1955) J. Chem. Phys., 23, p. 1841
  • Mulliken, (1955) J. Chem. Phys., 23, p. 2338
  • Mulliken, (1955) J. Chem. Phys., 23, p. 2343
  • Mulliken, (1962) J. Chem. Phys., 36, p. 3428
  • Roby, Quantum theory of chemical valence concepts (1974) Molecular Physics, 27, p. 81
  • Roby, (1974) Queen's Papers Pure Appl. Math., 40, p. 100
  • Armstrong, Perkins, Stewart, Bond indices and valency (1973) Journal of the Chemical Society, Dalton Transactions, p. 838
  • Jug, (1977) J. Am. Chem. Soc., 99, p. 7800
  • Jug, (1978) J. Am. Chem. Soc., 100, p. 6581
  • Jug, (1984) Croat. Chem. Acta, 57, p. 941
  • Mayer, (1983) Chem. Phys. Lett., 97, p. 270
  • Mayer, (1985) Theor. Chim. Acta, 67, p. 315
  • Löwdin, Quantum Theory of Many-Particle Systems. I. Physical Interpretations by Means of Density Matrices, Natural Spin-Orbitals, and Convergence Problems in the Method of Configurational Interaction (1955) Physical Review, 97, p. 1474
  • Coleman, (1963) Rev. Mod. Phys., 35, p. 668
  • Davidson, (1976) Reduced Density Matrices in Quantum Chemistry, , Academic Press, New York
  • McWeeny, Sutcliffe, (1976) Methods of Molecular Quantum Mechanics, , Academic Press, New York
  • Wiberg, (1968) Tetrahedron, 24, p. 1083
  • Pople, Beveridge, (1970) Approximate Molecular Orbital Theory, , McGraw-Hill, New York
  • Natiello, Medrano, (1984) Chem. Phys. Lett., 105, p. 180
  • Natiello, Reale, Medrano, A generalized formalism of the quantum theory of valence and bonding (1985) Journal of Computational Chemistry, 6, p. 108
  • Medrano, Reale, Bochicchio, (1986) J. Mol. Struct. (Theochem), 135, p. 117
  • von Neumann, (1932) Mathematical Foundations of Quantum Mechanics, , Springer, Berlin
  • Coleman, Reduced density operators and theN-particle problem (1978) International Journal of Quantum Chemistry, 13, p. 67
  • Bochicchio, Medrano, (1989) J. Mol. Struct. (Theochem), 201, p. 177
  • Bochicchio, Medrano, The use of a transportable Fourier transform infrared (FTIR) spectrometer for the direct measurement of solvents in breath and ambient air--I: Methanol. (1989) Am Ind Hyg Assoc J, 77, p. 499
  • Bochicchio, Medrano, Some new properties of the reduced density operator and derivation of molecular electronic entropy (1988) Journal of Molecular Structure: THEOCHEM, 169, p. 33
  • Szabo, Oustlund, (1982) Modern Quantum Chemistry: Introduction to Advanced Electronic Theory, , MacMillan, New York
  • Medrano, Bochicchio, (1989) J. Mol. Struct. (Theochem), 200, p. 463
  • Bochicchio, (1991) J. Mol. Struct. (Theochem), 228, p. 227
  • Löwdin, On the axioms of quantum theory formulated as a trace algebra (1982) International Journal of Quantum Chemistry, 21, p. 275
  • Stradella, Villar, Castro, (1986) Theor. Chim. Acta, 70, p. 67
  • Bochicchio, Reale, Medrano, (1989) Phys. Rev., Ser. B, 40, p. 7186
  • Halgren, Lipscomb, Approximations to Self-Consistent Field Molecular Wavefunctions (1972) Proceedings of the National Academy of Sciences, 69, p. 652
  • Halgren, Lipscomb, Self-consistent-field wavefunctions for complex molecules. The approximation of partial retention of diatomic differential overlap (1973) The Journal of Chemical Physics, 58, p. 1569
  • Ruedenberg, (1962) Rev. Mod. Phys., 34, p. 326
  • D.A. Micha, personal communication, 1987

Citas:

---------- APA ----------
(1991) . Quantum statistical nature of the chemical bond. Part I. Theoretical framework of population analysis and application to SCF closed shell wavefunctions. Journal of Molecular Structure: THEOCHEM, 228(C), 209-225.
http://dx.doi.org/10.1016/0166-1280(91)90058-R
---------- CHICAGO ----------
Bochicchio, R.C. "Quantum statistical nature of the chemical bond. Part I. Theoretical framework of population analysis and application to SCF closed shell wavefunctions" . Journal of Molecular Structure: THEOCHEM 228, no. C (1991) : 209-225.
http://dx.doi.org/10.1016/0166-1280(91)90058-R
---------- MLA ----------
Bochicchio, R.C. "Quantum statistical nature of the chemical bond. Part I. Theoretical framework of population analysis and application to SCF closed shell wavefunctions" . Journal of Molecular Structure: THEOCHEM, vol. 228, no. C, 1991, pp. 209-225.
http://dx.doi.org/10.1016/0166-1280(91)90058-R
---------- VANCOUVER ----------
Bochicchio, R.C. Quantum statistical nature of the chemical bond. Part I. Theoretical framework of population analysis and application to SCF closed shell wavefunctions. J. Mol. Struct. THEOCHEM. 1991;228(C):209-225.
http://dx.doi.org/10.1016/0166-1280(91)90058-R