Can the electronegativity equalization method predict spectroscopic properties?

• IR spectroscopic quantities derived from the electronegativity equalization method.
• EEM cannot reproduce DFT reference data for these spectroscopic quantities.
• Impact on development of polarizable and reactive force-field models is discussed.

The electronegativity equalization method is classically used as a method allowing the fast generation of atomic charges using a set of calibrated parameters and provided knowledge of the molecular structure. Recently, it has started being used for the calculation of other reactivity descriptors and for the development of polarizable and reactive force fields. For such applications, it is of interest to know whether the method, through the inclusion of the molecular geometry in the Taylor expansion of the energy, would also allow sufficiently accurate predictions of spectroscopic data. In this work, relevant quantities for IR spectroscopy are considered, namely the dipole derivatives and the Cartesian Hessian. Despite careful calibration of parameters for this specific task, it is shown that the current models yield insufficiently accurate results.

Graphical AbstractFigure optionsDownload as PowerPoint slide