多硼酸盐在硼酸盐水溶液中的研究：拉曼和密度泛函理论研究。

Polyborates in aqueous borate solution: a Raman and DFT theory investigation.

机构信息

CAS Key Laboratory of Salt Lake Resources and Chemistry, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining, PR China.

出版信息

Spectrochim Acta A Mol Biomol Spectrosc. 2011 Dec;83(1):82-7. doi: 10.1016/j.saa.2011.07.081. Epub 2011 Jul 30.

DOI:10.1016/j.saa.2011.07.081

PMID:21955949

Abstract

The geometries, energies and vibrational frequencies of various polyborates in both gaseous and aqueous phase were calculated at the B3LYP/aug-cc-pVDZ level. The calculated total symmetrical stretching Raman shifts of B(OH)(3), B(OH)(4)(-), B(2)O(OH)(4), B(2)O(OH)(5)(-), B(2)O(OH)(6)(2-), B(3)O(3)(OH)(3), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(3)O(3)(OH)(6)(3-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-) were assigned to 877.40, 735.33, 785.22, 792.90, 696.79, 587.72, 599.06, 740.16, 705.01, 551.67 and 521.04cm(-1), respectively. The results can be used as the characteristic frequency for polyborates in aqueous phase at room temperature. At least six types of polyborates B(OH)(3), B(OH)(4)(-), B(3)O(3)(OH)(4)(-), B(3)O(3)(OH)(5)(2-), B(4)O(5)(OH)(4)(2-) and B(5)O(6)(OH)(4)(-), occur in aqueous solutions at ambient temperature. The chemical species distribution and the relevant interaction mechanisms among polyborates in the solutions were also suggested.

摘要

采用 B3LYP/aug-cc-pVDZ 方法计算了气态和水相中的各种多硼酸盐的几何形状、能量和振动频率。计算了 B(OH)(3)、B(OH)(4)(-)、B(2)O(OH)(4)、B(2)O(OH)(5)(-)、B(2)O(OH)(6)(2-)、B(3)O(3)(OH)(3)、B(3)O(3)(OH)(4)(-)、B(3)O(3)(OH)(5)(2-)、B(3)O(3)(OH)(6)(3-)、B(4)O(5)(OH)(4)(2-)和 B(5)O(6)(OH)(4)(2-)的总对称伸缩拉曼位移分别为 877.40、735.33、785.22、792.90、696.79、587.72、599.06、740.16、705.01、551.67 和 521.04cm(-1)。这些结果可作为室温下水相多硼酸盐的特征频率。在环境温度下，水溶液中至少存在六种类型的多硼酸盐，即 B(OH)(3)、B(OH)(4)(-)、B(3)O(3)(OH)(4)(-)、B(3)O(3)(OH)(5)(2-)、B(4)O(5)(OH)(4)(2-)和 B(5)O(6)(OH)(4)(2-)。还提出了溶液中多硼酸盐的化学物质分布和相关相互作用机制。