Novel methods of partial atomic charge determination are of interest in both experimental and theoretical chemistry due to their usefulness in modeling dipole moments, auto-correlation functions, charge disparity, understanding of dispersion, benchmark of classical MD simulations, and electrostatic potential energy surface mapping. Currently, experimental techniques such as IR and Raman spectroscopy as well as physical dipole moment measurements are relied upon to establish a correspondence between theoretical and experimental results, but these techniques are indirect and unable to finely map electrostatic potential from theory to experiment. X-ray crystallography was used to refine atomic models of various small molecules and partial atomic charges were calculated for each molecule using refined partial occupancies. Gas phase Mulliken, NBO, and ESP charges were calculated using the Gaussian suite for each molecule, as well as condensed phase Lowdin charges. The experimentally determined partial atomic charges were found to exhibit satisfactory agreement with theoretical charges from quantum mechanical calculations, particularly charges obtained from CHELPG and condensed phase Lowdin methods.

Calculations of partial atomic charges from partial occupancy refinement of X-Ray crystallographic models, with correspondence to <i>ab-initio</i> methods

ACS Spring Meeting 2021

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Calculations of partial atomic charges from partial occupancy refinement of X-Ray crystallographic models, with correspondence to ab-initio methods