从头算研究 Li[B(OH)] 溶液中的离子缔合物种和缔合过程。

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

机构信息

Key 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.

The Institute of Chemical Physics, School of Science, and School of Aerospace Science and Engineering, Beijing Institute of Technology, Beijing 100081, China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2019 Apr 15;213:423-429. doi: 10.1016/j.saa.2019.01.026. Epub 2019 Jan 15.

DOI:10.1016/j.saa.2019.01.026

PMID:30731254

Abstract

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.

摘要

本文通过从头计算研究了在 Li[B(OH)]溶液中，v-B(OH)带的光谱特性决定因素，包括耦合效应、氢键效应和直接接触效应。水的离解与[B(OH)]的耦合效应对溶剂共享离子对（SIP）和单齿接触离子对（MCIP）中的 v-B(OH)影响较大，但对双齿接触离子对（BCIP）影响较小。水分子倾向于水合到 B(OH)的第一球和[Li(HO)]的外球之间的中间位置，并且对离子对中的 v-B(OH)有不同的影响。直接接触效应和极化效应导致 MCIP 中 v-B(OH)的红移 19.7 cm，BCIP 中蓝移 0.4 cm。还通过脱水过程中 v-B(OH)的拉曼光谱演化介绍了 Li[B(OH)]溶液中的缔合过程。