Department of Chemistry , Colorado State University , Fort Collins , Colorado 80523 , United States.
Department of Chemistry , University of Colorado at Denver , Denver , Colorado 80217 , United States.
J Phys Chem A. 2019 Nov 14;123(45):9781-9790. doi: 10.1021/acs.jpca.9b07628. Epub 2019 Nov 5.
Room-temperature-attenuated total reflection-Fourier transform infrared (FTIR) spectra of the structurally characterized crystalline lithium salt Li(HO)(BF), which contains a cyclic symmetry (HO) cluster, and several partially or completely deuterated isotopologs, suggest the following conclusions: (i) B and E normal modes gave rise to two distinguishable ν(OH) bands, separated by 42 cm, two distinguishable ν(OH) bands, separated by 13 cm, and two distinguishable δ(HOH) bands, separated by 19 cm, in the FTIR spectrum of Li(HO)(BF); (ii) B and E normal modes gave rise to two distinguishable ν(OD) bands separated by 20 cm in the FTIR spectrum of Li(DO)(BF); (iii) coupling between ν(OH) and ν(OH) normal modes or between ν(OD) and ν(OD) normal modes is weak, but finite, and resulted in shifts of 4-10 cm for the respective bands in the spectra of Li(HO)(BF) vs Li(HOD)(DO)(BF) or in the spectra of Li(DO)(BF) vs Li(HOD)(HO)(BF); and (iv) a δ(DOD) band for an (DO) cluster, at ca. 1202 cm, was observed for the first time. In addition, FTIR spectra of the lithium salt containing cyclic [(HOD)(HO)] or [(HOD)(DO)] clusters are the first examples in which bands that are unambiguously assigned to both HO-D···O and DO-H···O hydrogen bonds in the same sample have been observed for a water tetramer.
室温衰减全反射-傅里叶变换红外（FTIR）光谱对结构表征的结晶锂盐 Li(HO)(BF) 进行了研究，该盐含有一个具有循环对称性的 (HO) 簇，以及几个部分或完全氘代的同位素。研究结果表明：(i) B 和 E 正则模态在 Li(HO)(BF) 的 FTIR 光谱中产生了两个可区分的 ν(OH) 带，它们之间的间隔为 42cm，两个可区分的 ν(OH) 带，间隔为 13cm，两个可区分的 δ(HOH) 带，间隔为 19cm；(ii) B 和 E 正则模态在 Li(DO)(BF) 的 FTIR 光谱中产生了两个可区分的 ν(OD) 带，间隔为 20cm；(iii) ν(OH) 和 ν(OH) 正则模态之间或 ν(OD) 和 ν(OD) 正则模态之间的耦合很弱，但有限，导致在 Li(HO)(BF) 与 Li(HOD)(DO)(BF) 或 Li(DO)(BF) 与 Li(HOD)(HO)(BF) 的光谱中，相应的带发生了 4-10cm 的位移；(iv) 首次观察到了一个约为 1202cm 的 (DO) 簇的 δ(DOD) 带。此外，含有环状 [(HOD)(HO)] 或 [(HOD)(DO)] 簇的锂盐的 FTIR 光谱是首次在同一样品中观察到明确归属于 HO-D···O 和 DO-H···O 氢键的带的例子，其中水四聚体。
