Hirshfeld partitioning of the electron density: Atomic dipoles and their relation with functional group properties

Atomic dipole moments, derived within the Hirshfeld partitioning of the molecular electron density, have been studied for compounds of the type HX and ClX, for a series of functional groups X frequently encountered in organic molecules. In the case of the HX compounds, the component of the atomic dipole moment on H along the axis connecting H with the central atom in X is found to be linearly correlated with the electronegativity of X, the hardness of X playing no significant role. In the case of the ClX compounds, the situation is less clear. However, evidence seems to point to the conclusion that for these compounds, also the group hardness plays an important role. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 463–469, 2003

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