Wild D A, Lenzer T
MPI für biophysikalische Chemie, Abteilung Spektroskopie und Photochemische Kinetik (10100), Am Fassberg 11, D-37077, Göttingen, Germany.
Phys Chem Chem Phys. 2005 Nov 21;7(22):3793-804. doi: 10.1039/b510923j. Epub 2005 Sep 22.
Clusters formed between a fluoride anion and several hydrogen sulfide molecules have been investigated via ab initio calculations at the MP2 level of theory, using Dunning's augmented correlation consistent basis sets. Optimised geometries, vibrational frequencies, and enthalpy changes for the ligand association reactions are presented for clusters with up to five H2S ligands interacting with a F- anion. The minimum energy structure for the 1:1 F(-)-H2S complex features proton transfer from the H2S to the F- anion, forming a planar C(s) symmetry FH...SH- structure. For the F(-)-(H2S)2 cluster, the FH...SH- core remains and is solvated by a perturbed H2S ligand. For the larger F(-)-(H2S)(3-5) clusters, in addition to the FH...SH(-)-(H2S)n cluster forms, other minima featuring a 'solvated F-' anion are predicted. Calculated infrared spectra for the minima of each cluster size are presented to aid in assigning spectra from future experimental studies.
通过在MP2理论水平上使用邓宁增强相关一致基组进行从头算计算，研究了氟阴离子与几个硫化氢分子之间形成的团簇。给出了多达五个H₂S配体与F⁻阴离子相互作用的团簇的优化几何结构、振动频率和配体缔合反应的焓变。1:1 F⁻-H₂S络合物的最低能量结构具有质子从H₂S转移到F⁻阴离子的特征，形成平面C(s)对称的FH...SH⁻结构。对于F⁻-(H₂S)₂团簇，FH...SH⁻核心保留并被一个受扰的H₂S配体溶剂化。对于更大的F⁻-(H₂S)₃₋₅团簇，除了FH...SH⁻-(H₂S)ₙ团簇形式外，还预测了其他以“溶剂化F⁻”阴离子为特征的极小值。给出了每个团簇尺寸极小值的计算红外光谱，以帮助从未来的实验研究中指定光谱。
