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Ab-initio investigation on ion-associated species and association process in Li[B(OH)4] solution
Fayan Zhu1, Hongyan Liu1, Wenqian Zhang1
1Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xingning 810008, China; Key Laboratory of Salt Lake Resources Chemistry of Qinghai Province, Qinghai Institute of salt Lakes, Chinese Academy of Science, Xining, 810008, China.
Abstract:
In this paper, the factors determining the spectroscopic characteristics of vsym-B(OH)4- band including coupling effect, hydrogen bonding effect, and direct contact effect in Li[B(OH)4] solutions are investigated by using ab initio calculation. The coupling effect between the liberations of water and [B(OH)4-] has a larger effect on vsym-B(OH)4- 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)4- and outer-sphere of [Li(H2O)4+] and has a different effect on vsym-B(OH)4- in ion pairs. The direct contact effect and polarization effect lead to 19.7 cm-1 red shift of vsym-B(OH)4- in MCIP, and 0.4 cm-1 blue shift in BCIP. The association process in Li[B(OH)4] solution was also introduced by using Raman spectral evolution of vsym -B(OH)4- in the dehydration process.
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