Anomalous energy yields in thermodynamic calculations: importance of accounting for pH-dependent organic acid speciation (original) (raw)

Acidities under the Perspective of Energy Decomposition Analysis

The journal of physical chemistry. A, 2017

The rationalization of acid/base behavior is a central concern for chemistry and related fields. In this work, we describe an alternative approach toward the understanding of gas phase acidities based on the localized molecular orbital energy decomposition analysis (LMOEDA) method. Upon partitioning the molecules (and the corresponding anions) over the X-OH (or X-O(-)) bond, we have observed a perfect correlation between the interaction energy of the two fragments and the acidity, as given by the energy difference between the anion and the neutral molecule. On the basis of this correlation, acidities could be interpreted according to the energy components provided by LMOEDA, namely, electrostatic, exchange repulsion, polarization, and dispersion. For example, alkyl groups increase the gas phase acidities of alcohols mainly due to electrostatic and polarization interactions. Carboxylic acids are stronger acids than alcohols through the ability of oxygen to stabilize the extra charge ...