Analysis of the delocalization in the topological theory of chemical bond

Abstract The topological analysis of the gradient field of the electron localization function provides a convenient theoretical framework for the partition of the molecular space into basins of attractors having a clear chemical meaning. The basin populations are evaluated by integrating the one-electron density over the basins. The variance of the basin population provides a measure of the delocalization. The behavior of the core C(X) and protonated valence basins V(X, H) populations were investigated. The analysis of the population variance in terms of cross-contributions is presented for aromatic and antiaromatic systems, hypervalent molecules and hydrogen-bonded complexes. For hypervalent molecules this analysis emphasizes the importance of the ionic resonance structures.

[1]  Axel D. Becke,et al.  A Simple Measure of Electron Localization in Atomic and Molecular-Systems , 1990 .

[2]  Bernard Silvi,et al.  CHARACTERIZATION OF ELEMENTARY CHEMICAL PROCESSES BY CATASTROPHE THEORY , 1997 .

[3]  P. Schleyer,et al.  Chemical bonding in hypervalent molecules. The dominance of ionic bonding and negative hyperconjugation over d-orbital participation , 1990 .

[4]  I. Mayer On bond orders and valences in the Ab initio quantum chemical theory , 1986 .

[5]  Reinhard Nesper,et al.  A New Look at Electron Localization , 1991 .

[6]  J. P. Malrieu,et al.  Localization and Delocalization in Quantum Chemistry , 1975 .

[7]  A.V. Kovalyov An O , 1995, Proceedings of Tenth International Symposium on Intelligent Control.

[8]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[9]  L. Salem The molecular orbital theory of conjugated systems , 1966 .

[10]  M. Huggins The Structure of Benzene , 1922, Nature.

[11]  R. Bader Comparison of Loge and Virial Methods of Partitioning Molecular Charge Distributions , 1975 .

[12]  Miss A.O. Penney (b) , 1974, The New Yale Book of Quotations.

[13]  R. Bader Atoms in molecules : a quantum theory , 1990 .

[14]  Andreas Savin,et al.  Topological analysis of the electron localization function applied to delocalized bonds , 1996 .

[15]  A. Becke Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[16]  E. Magnusson Hypercoordinate molecules of second-row elements : d functions or d orbitals ? , 1990 .

[17]  A. Savin,et al.  Classification of chemical bonds based on topological analysis of electron localization functions , 1994, Nature.

[18]  R. Daudel Quantum Theory of the Chemical Bond , 1974 .

[19]  I. Mayer Bond orders and valences in the SCF theory: a comment , 1985 .

[20]  J. Ángyán,et al.  COVALENT BOND ORDERS AND ATOMIC VALENCE INDICES IN THE TOPOLOGICAL THEORY OF ATOMS IN MOLECULES , 1994 .

[21]  R. Mcweeny,et al.  Methods Of Molecular Quantum Mechanics , 1969 .