Hydridic-to-protonic interactions in unconventional dihydrogen bonding influence the structure, reactivity, and selectivity in solution and in the solid state. In this study, the structure, stability, and Raman spectra of BH₄^– hydrated clusters, [BH₄(H₂O)_n]⁻ (n = 1–8, 10, 12, 14, 16) are systematically investigated using density functional theory (DFT) at the wB97XD/6-311++g(3df,3pd) basis set level. The successive microhydration process is described to illustrate in detail the changes in dihydrogen bonding with increasing hydration cluster size. The results of DFT calculations indicate that seven or eight water molecules hydrate BH₄^– with a total of 12 dihydrogen bonds in the tetrahedral edge or tetrahedral corner forms, and a maximum of six water molecules in the tetrahedral-edge form. Raman spectra of [BH₄(H₂O)_n]⁻ show a blue shift in the B–H stretching band due to hydration. Car–Parrinello molecular dynamics simulations verify strong BH₄^– water interactions. The hydration number of BH₄^– is 6.7, with a hydration B–O(W) distance of 3.40 Å, and each hydrogen in BH₄^– bonds with 2.66 hydrogen atoms from water.

中文翻译：

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BH ₄ ^–的微水合：二氢键，结构，稳定性和拉曼光谱

非常规二氢键中的氢-质子相互作用影响溶液和固态的结构，反应性和选择性。在这项研究中，结构，稳定性，和BH的拉曼光谱₄ ^-水合集群，[BH ₄（H ₂ O）_Ñ ] ^- （Ñ = 1-8，10，12，14，16）被系统地研究了使用密度在wB97XD / 6-311 ++ g（3df，3pd）基础集级别上的功能理论（DFT）。描述了连续的微水化过程，以详细说明随着水合簇尺寸的增加，二氢键的变化。DFT计算的结果表明，七个，八水分子滋润BH ₄ ^-在四面体边缘或四面体角形式中总共有12个二氢键，而在四面体边缘形式中最多有六个水分子。[BH ₄（H ₂ O）_n ] ^-的拉曼光谱显示，由于水合作用，B–H拉伸带发生蓝移。Car–Parrinello分子动力学模拟验证了BH ₄^与水之间的强相互作用。BH ₄ ^–的水合数为6.7，水合B–O（W）距离为3.40Å，BH ₄ ^–中的每个氢原子均与水中的2.66个氢原子键合。