Atomic partial charge model in chemistry: chemical accuracy of theoretical approaches for diatomic molecules

Abstract

Abstract Atomic partial charges cannot be physically measured but they play a significant role in many chemical theories and theoretical models. Therefore, they are, evaluated from experimentally acquired properties or calculated by quantum chemistry computational methods. This study is focused on determining chemical accuracy of various theoretical methods of computing atomic partial charges based on quantum chemistry. Values of gas-phase atomic partial charges were acquired by Mulliken (MUL) population analysis, natural bond analysis (NBO), Merz-Singh-Kollman (MSK) scheme, and atomic polar tensor (APT) charges computed considering Density Functional Theory and ab initio Møller-Plesset up to the second order levels. Correlations between the calculated values were determined by principal component analysis (PCA) and further confirmed by linear regression. The best agreement between experimentally evaluated atomic partial charges and theoretical values was obtained with the MSK scheme.