Introduction: The Role of the Electrostatic Potential in Chemistry

  • Peter Politzer
  • Donald G. Truhlar


The electrostatic potential at a point \(\vec r\) in the vicinity of an atomic or molecular system having an electronic density function ρ(\(\vec r\) ) is given, in atomic units,* by
$${V^{ES}}\left( {\overrightarrow r } \right) = \sum\limits_A {\frac{{{Z_A}}}{{\left| {{{\overrightarrow R }_A} - \overrightarrow r } \right|}}} - \int {\frac{{\rho \left( {\overrightarrow {r'} } \right)\overrightarrow {dr'} }}{{\left| {\overrightarrow {r'} - \overrightarrow r } \right|}}}$$
where ZA is the charge on nucleus A, located at \({\vec R_A}\) A. The two terms on the right side of equation (1) correspond, respectively, to the nuclear and electronic contributions to the potential. As can be seen, they have opposite signs and accordingly opposite effects; VES (\(\vec r\)) represents the net result at any point \(\vec r\). The electrostatic potential is a real physical property, which is rigorously defined by equation (1). It is exactly equal in magnitude to the electrostatic (coulombic) interaction energy between the static (i.e., unperturbed) charge distribution of the system and a positive unit point charge located at \(\vec r\).


Electrostatic Potential Electrostatic Molecular Potential Electronic Density Function Positive Unit Atomic Electron Density 
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Copyright information

© Springer Science+Business Media New York 1981

Authors and Affiliations

  • Peter Politzer
    • 1
  • Donald G. Truhlar
    • 2
  1. 1.Department of ChemistryUniversity of New OrleansNew OrleansUSA
  2. 2.Department of Chemistry and Chemical Physics ProgramUniversity of MinnesotaMinneapolisUSA

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