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Density Functionals of Chemical Bonding

By Mihai V. Putz


The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems

Topics: Review
Publisher: Molecular Diversity Preservation International (MDPI)
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Provided by: PubMed Central

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  1. (1985). A Group Electronegativity Method with Pauling Units,
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  3. (1982). A new Gradient Expansion of the Exchange Energy to Be Used in Density Functional Calculations on Atoms,
  4. (1988). A Physical Basis for the VSEPR Model of Molecular Geometry,
  5. (1993). A Practical Guide to Data Analysis for Physical Science Students,
  6. (1990). A Simple Measure of Electron Localization in Atomic and Molecular Systems,
  7. A Simplification of the Hartree-Fock Method,
  8. (2008). Absolute and Chemical Electronegativity and Hardness,
  9. (1983). Absolute Hardness: Companion Parameter to Absolute Electronegativity,
  10. (1986). Accurate and Simple Density Functional for the Electronic Exchange Energy: Generalized Gradient Approximation,
  11. (1980). Accurate Spin-Dependent Electron Liquid Correlation Energies for Local Spin Density Calculations: A Critical Analysis,
  12. (1999). Alternative Definition of Exchange-Correlation Charge in Density Functional Theory,
  13. (1986). An Application of Correlation Energy Density Functionals to Atoms and Molecules, Theor Chim Acta
  14. (2007). Anatomy of bond formation. Bond length dependence of the extent of electron sharing in chemical bonds from the analysis of domain-averaged Fermi holes, Faraday Discuss.,
  15. (1989). Application of Generalized Exchange Local-Spin-Density-Functional Theory: Electronegativity, Hardness,
  16. (2007). Can Quantum-Mechanical Description of Chemical Bond Be Considered Complete?,
  17. (1994). Classification of the Chemical Bonds Based on Topological Analysis of Electron Localization Functions,
  18. (1986). Completely Numerical Calculations on Diatomic Molecules in the Local-Density Approximation,
  19. (2003). Contributions within Density Functional Theory with Applications to Chemical Reactivity Theory and Electronegativity,
  20. (1988). Correlation Energy of an Inhomogeneous Electron Gas: A Coordinate-Space,
  21. (1986). Density Functional Calculations of Molecular Bond Energies,
  22. (1989). Density Functional Theory of Atoms and Molecules,
  23. (1996). Density Functional Theory of Electronic Structure,
  24. (1998). Density Functional Theory of One-Dimension Two-Particle Systems,
  25. (1990). Density Functional Theory,
  26. (1986). Density-Functional Approximation for the Correlation Energy of the Inhomogeneous Electron Gas,
  27. (1991). Density-Functional Exchange Correlation Through Coordinate Scaling in Adiabatic Connection and Correlation Hole,
  28. (1996). Density-Functional Exchange Identity from Coordinate Scaling,
  29. (1988). Density-Functional Exchange-Energy Approximation with Correct Asymptotic Behavior,
  30. (1991). Density-Functional Formalism and the Two-Body Problem,
  31. (1999). Density-Functional Formulas for Atomic Electronic Energy Components
  32. (1994). Density-Functional Theory as an Example for the Construction of Stationarity Principles,
  33. (1988). Density-Functional Theory for Ensembles of Fractionally Occupied States. II. Applications to the He Atom, Phys. Rev. A
  34. (1988). Density-Functional Theory for Ensembles of Fractionally Occupied States.I. Basic Formalism,
  35. (1995). Density-Functional Theory Using an Optimized Exchange-Correlation Potential,
  36. (1992). Derivatives of the Local-Density-Functional Total Energy when the Local Potential is Fitted,
  37. (1988). Development of the Colle-Salvetti Correlation-Energy Formula into a Functional of the Electron Density,
  38. (1992). Differential Equations for the Square Root of the Electronic Density
  39. (2000). Direct Space Representation of the Metallic
  40. (1987). Electron Affinities in the Self-Interactions-Corrected Local Spin Density Approximation,
  41. (1998). Electron Affinity in Density-Functional Theory in the Local Spin-Density Approximation,
  42. Electron Density Theory of Many-Electron Systems,
  43. (2004). Electron Localizability Indicator for Correlated Wavefunctions.
  44. (2006). Electron Localization Function at the Correlated Level,
  45. (1978). Electronegativity: the Density Functional Viewpoint,
  46. (2000). Ensuring Proper Short-Range and Asymptotic Behavior of the Exchange-Correlation Kohn-Sham Potential by Modeling with a Statistical Average of Different Orbital Model Potential,
  47. (1996). Exact Local Exchange Potential from Fock Equations at Vanishing Coupling Constant, and δTc / δn from Wave-Function Calculations at Full Coupling Constant, Phys. Rev. A
  48. (1986). Exchange and Correlation Energy in a Nonuniform Fermion Fluid,
  49. (1991). Exchange and Exchange-Correlation Functionals Based on the Gradient
  50. (1990). Exchange-Correlation Functional for Atoms and Molecules,
  51. (1991). Exchange-Energy Density Functional: Reparametrization of Becke’s Formula and Derivation of Second-Order Gradient Correction, Phys. Rev. A
  52. (1999). Expansion of the Density-Functional Energy Components Ec and Tc
  53. (1986). Exponential Approximation for the Density Matrix and the Wigner’s Distribution, Chem Phys.
  54. (1991). Formulation of N-and V-Representable Density-Functional Theory.
  55. (2001). Foundations for a Theory of the Chemical Field.
  56. (1997). Fractional Occupation Numbers in Density-Functional Theory,
  57. (1994). From Electron Densities to Kohn-Sham Kinetic Energies, Orbital Energies, Exchange-Correlation Potentials, and Exchange-Correlation Energies,
  58. (1987). Gaussian and Other Approximations to the First-Order Density Matrix of Electronic System, and the Derivation of Various Local-Density-Functional-Theories,
  59. (1988). Generalized Exchange Local-Spin-Density-Functional Theory: One-Electron Energies and Eigenvalues, Collection Czechoslovak Chem. Commun.
  60. (1996). Generalized Gradient Approximation Made Simple,
  61. (1996). Generalized Gradient Correction for Exchange: Deduction from the Oscillator Model,
  62. (1991). Generalized Local-Spin-Density-Functional Theory,
  63. (1988). Generalized-Exchange Local-Spin-Density-Functional Theory: Calculation and Results for Non-Self-Interaction-Corrected and Self-Interaction-Corrected Theories, Phys. Rev. A
  64. (1994). Generalized-Gradient-Approximation Description of Band Splittings
  65. (2006). Global and Local Indicators of Chemical Bonding,
  66. (1996). Hohenberg-Kohn Density-Functional-Theory as an Implicit Poisson equation for Density Changes from Summed Fragment Densities,
  67. (1964). Inhomogeneous Electronic Gas,
  68. (1983). Introduction to the Chemistry of Fractionally Charged Atoms: Electronegativity,
  69. (1996). Kinetic-Energy Density Functional: Atoms and Shell structure,
  70. (1987). Kinetic-Energy Functionals via Padé Approximations,
  71. (1999). Kinetic-Energy Systems, Density Scaling, and Homogeneity Relations
  72. (1998). Kohn-Sham Equations for Multiplets, Phys. Rev. A
  73. (1992). Local Exchange-Correlation Functional: Numerical Test for Atoms and Ions,
  74. (1996). Local-Density Approximation, Hierarchy of Equations, Functional Expansion, and Adiabatic Connection in Current-Density-Functional Theory,
  75. (1987). Local-Density-Functional Approximation for Exchange-Correlation Potential. Application of the Self-Consistent and Statistical Exchange-Correlation Parameters to the Calculation of the Electron Binding Energies, Theor. Chim Acta
  76. (1990). Local-Density-Functional Total Energy Gradients
  77. (2005). Markovian Approach of the Electron Localization Functions,
  78. (1994). Maximum Entropy Analysis of the Electron-Pair Density in
  79. Maximum Hardness Index of Quantum Acid-Base Bonding,
  80. (1984). Molecular Correlation Energies Obtained with a Nonlocal Density Functional,
  81. (1992). Molecules, Solids, and Surfaces: Applications of the Generalized Gradient Approximation for Exchange and Correlation,
  82. (1988). New Nonlocal Exchange-Energy Functional from a KineticEnergy-Density Padé-Approximant Model, Phys. Rev. A
  83. (1987). Non-Local Effects on Atomic and Molecular Correlation Energies Studies with a Gradient-Corrected Density Functional,
  84. (1978). Nonlocal Approximation to the Exchange Potential and Kinetic Energy of an Inhomogeneous Electron Gas,
  85. (1990). Nonlocal Wigner-Like Correlation-Energy Density Functional Through Coordinate Scaling,
  86. (1998). Nonlocality of the Density Functional for Exchange and Correlation: Physical Origins and Chemical Consequences,
  87. (1990). Nonnuclear Attractors in the LI2
  88. (1990). Nonuniform Coordinate Scaling Requirements
  89. (2005). On the Accuracy of Numerical Hartree–Fock Energies,
  90. (2004). On The Applicability of The HSAB Principle through The Use of Improved Computational Schemes for Chemical Hardness Evaluation,
  91. (1986). On the Formulation of the Hohenberg-Kohn-Sham Theory,
  92. (1982). On the Functional Derivative of the Kinetic Energy Density Functional,
  93. (1986). Phase-Space Approach to the Exchange Energy Functional of DensityFunctional Theory,
  94. (1978). Proof that i i n
  95. (1992). Quantities Ts[n] and Tc[n]
  96. (1992). Quantum Mechanics,
  97. (2008). Quantum Perspectives on the Nature of the Chemical Bond,
  98. (1965). Self-Consistent Equations Including Exchange and Correlation Effects,
  99. (1994). Self-Consistent-Field Calculations of Atoms and Ions Using a Modified Local-Density Approximation,
  100. (1972). Self-Consistent-Field Xα Cluster Method for Polyatomic Molecules and Solids,
  101. (1981). Self-Interaction Correction to Density-Functional Approximations for Many-Electron System,
  102. Semiclassical Electronegativity and Chemical Hardness.
  103. (2000). Sigma-pi Separation of the Electron Localization Function
  104. (1981). Sixth-Order Term of the Gradient Expansion of the Kinetic-Energy Density Functional,
  105. (1984). Slater Sum in One Dimension: Explicit Kinetic Energy Functional,
  106. (1970). Solutions of the Simplified Self-Consistent Field for All Atoms of the Periodic System of elements from Z=2 to Z=92, Adam Hilger Ltd.,
  107. (2000). Statistics and Chemometrics for Analytical Chemistry, fourth edition,
  108. (1999). Strictly Correlated Electrons
  109. (2000). Sum Rules for Exchange and Correlation Potentials,
  110. (1988). Symmetry and Spin Density Functional Theory,
  111. (2006). Systematic Formulation for Electronegativity and Hardness and Their Atomic Scales within Density Functional Softness Theory.
  112. (1985). The Constrained Search Formulation of Density Functional Theory in ”Density Functional Methods
  113. (1998). The Development of New Exchange-Correlation Functionals,
  114. (1995). The Maximum Hardness Principle in the GyftpoulosHatsopoulos Three-Level Model for an Atomic or Molecular Species and Its Positive and Negative Ions,
  115. (1981). The Role of Single-Particle Density
  116. (1987). The Three-Dimensional Kinetic Energy Density Functional Compatible with the Exact Differential Equation for its Associated Tensor,
  117. (1991). Theorem for Functional Derivatives in Density-Functional Theory,
  118. (1934). Uber die Zuordnung von Wellen Funktionen und Eigenwerter zu den Einzelnen Elektronen Eines Atom,
  119. (2007). Unifying Absolute and Chemical Electronegativity and Hardness Density Functional Formulations through the Chemical Action Concept,
  120. (1991). V-Representability for Systems of a Few Fermions, Phys. Rev. A
  121. (1991). V-Representability for Systems with Low Degeneracy,
  122. (2000). Variational Principles for Describing Chemical Reactions: the Fukui Function and Chemical Hardness Revisited,
  123. (1998). Viral Exchange-Correlation Energy Density in Hooke’s Atom,

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