Microsolvation of LiBO₂ in water: anion photoelectron spectroscopy and ab initio calculations

Abstract

The microsolvation of LiBO2 in water was investigated by conducting anion photoelectron spectroscopy and ab initio studies on the LiBO2(H2O)n(-) (n = 0-5) clusters. By comparing calculations with experiments, the structures of these clusters and their corresponding neutrals were assigned, and their structural evolutions were revealed. During the anionic structural evolution with n increasing to 5, hydroxyborate and metaborate channels were identified and the metaborate channel is more favorable. For the hydroxyborate structures, the anionic Li(+)-BO2(-) ion pair reacts with a water molecule to produce the LiBO(OH)2(-) moiety and three water molecules tend to dissolve this moiety. In the metaborate channel, two types of solvent-separated ion pair (SSIP) geometries were determined as the ring-type and linear-type. The transition from the contact ion pair (CIP) to the ring-type of SSIP starts at n = 3, while that to the linear-type of SSIP occurs at n = 4. In neutral LiBO2(H2O)n clusters, the first water molecule prefers to react with the Li(+)-BO2(-) ion pair to generate the LiBO(OH)2 moiety, analogous to the bulk crystal phase of α-LiBO2 with two O atoms substituted by two OH groups. The Li-O distance in the LiBO(OH)2 moiety increases with the increasing number of water molecules and elongates abruptly at n = 4. Our studies provide new insight into the initial dissolution of LiBO2 salt in water at the molecular level and may be correlated to the bulk state.

Microsolvation of sodium acetate in water: Anion photoelectron spectroscopy and ab initio calculations

“…Special attention has been paid to investigate the transition between salt contact ion pairs (CIPs) and solvent-separated ion pairs (SSIPs) in water, 13,30 as well as the correlation of salt effects with the Hofmeister series. 31,32 Previously, our group has employed anion photoelectron spectroscopy and theoretical calculations to investigate the microsolvation of a number of salts such as NaBO 2 , 33 LiBO 2 , 34 LiI, CsI, 35 NaCl, 36 and Li 2 SO 4 37 in water. Sodium acetate (CH 3 COONa, NaOAc) is an important salt that is widely used in the industry and our daily life.…”

Emergence of Solvent-Separated Na+–Cl– Ion Pair in Salt Water: Photoelectron Spectroscopy and Theoretical Calculations

“…They also play diverse roles in the Hofmeister series and biochemical systems. − To understand the effects of salt ions on water as well as their correlation with the Hofmeister series, , it is especially important to investigate the contact ion pair (CIP) to solvent-separated ion pair (SSIP) transition in salt water , and the arrangement of water molecules in the first solvation shell. Many efforts have been devoted to understanding the solvation of salts in water. − …”

Raman spectroscopy and ab initio quantum chemical calculations of ion association behavior in calcium nitrate solution

“…The ωB97XD functional is the main consideration for weak‐interaction cluster systems, which has been shown to perform extraordinarily well on describing dispersion interaction and long range correlations . So in this paper, geometry optimizations of Ca(NO 3 ) 2 clusters were carried out by using density functional theory method at ωB97XD functional and the 6‐311++G(d, p) basis set level .…”