ATOMIC DIPOLE MOMENT CORRECTED HIRSHFELD POPULATION METHOD

作者：Lu Tian; Chen Feiwu^*

来源：Journal of Theoretical and Computational Chemistry, 2012, 11(1): 163-183.

DOI：10.1142/S0219633612500113

• Atomic charge
• population analysis
• atomic dipole moment correction
• preservation of the molecular dipole moment
• Hirshfeld

Charge preservation is a necessary condition in population analysis. However, one such constraint is not enough to solve the arbitrariness involved in the population analysis such as Hirshfeld population. This arbitrariness results in too small Hirshfeld charges and poor reproducibility of molecular dipolar moments. In this article, the preservation of the molecular dipole moment is imposed upon the Hirshfeld population analysis as another constraint to improve the original Hirshfeld charges. In the scheme each atomic dipolar moment defined by the deformation density is expanded as contributions from all atoms in the molecule. The corresponding correction charges are then accumulated for each atom together with the original Hirshfeld charge as the predicted charge. All computed charges are generally larger than Hirshfeld charges, independent of basis set, and have very good electrostatic potential reproducibility and high correlation with the charges derived from the electrostatic potential fitting.

• 出版日期2012-2
• 单位北京科技大学