Structures and Electronic Properties of Anions XO- (X = Li, B, N, F, Na, Al, P, and Cl) from a Computational Study

Abstract

The electronic and molecular structures of oxygen containing anion constructed by model XO- (X = Li, B, N, F, Na, Al, P, and Cl) have been studied in detail using ab initio MP2 and QCISD(T) methods with the aug-cc-pVDZ basis set. Our findings suggest that the p-donation character initiated by Cl atom exists in bond of Cl-O, and a triple bond can be viewed approximately for the bonding in the BO- ion. As compared with the formation of LiO-, the X-O (X = substituents) stretching frequency is slightly red-shifted in the F...O- interaction but slightly blue-shifted in both B...O- and N...O- interactions, in which the strength of the NO- prevails over the BO-. In addition, for the anions electron-deficient substituents can strengthen the ionization energy (IE) while the stronger metallic substituent results in higher proton affinity (PA). Meanwhile, both radial distribution function (RDF) and mean square displacement (MSD) based on molecular dynamics (MD) simulations are also performed to predict reactivity of the title anions by describing the behavior of H atom in the HOX molecules under the larger amounts.