Ab-initio investigation on ion-associated species and association process in Li[B(OH)] solution.

In this paper, the factors determining the spectroscopic characteristics of v-B(OH) band including coupling effect, hydrogen bonding effect, and direct contact effect in Li[B(OH)] solutions are investigated by using ab initio calculation. The coupling effect between the liberations of water and [B(OH)] has a larger effect on v-B(OH) in solvent-shared ion pair (SIP) and monodentate contact ion pair (MCIP), but the smaller effect in bidentate contact ion pair (BCIP). Water molecule tends to hydrate to the middle position between the first sphere of B(OH) and outer-sphere of [Li(HO)] and has a different effect on v-B(OH) in ion pairs. The direct contact effect and polarization effect lead to 19.7 cm red shift of v-B(OH) in MCIP, and 0.4 cm blue shift in BCIP. The association process in Li[B(OH)] solution was also introduced by using Raman spectral evolution of v -B(OH) in the dehydration process.