Structural and spectral consequences of ion pairing. 4. Theoretical study of BF sub 4 sup minus M sup + (M = Li, Na, K, and Rb)

Journal Article · Thu Nov 15 04:00:00 EST 1990 · Journal of Physical Chemistry; (USA)

DOI:https://doi.org/10.1021/j100386a008· OSTI ID:6081147

Francisco, J S ^[1]; Williams, I H ^[2]

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1. Wayne State Univ., Detroit, MI (USA)
2. Univ. of Bath (England)

Ion pairs of BR{sub 4}{sup {minus}} anion with the cations Li{sup +}, Na{sup +}, K{sup +}, and Rb{sup +} have been studied by ab initio quantum-chemical methods. Optimized geometries for monodentate, bidentate, and tridentate structures have been determined at the HF/3-21 G and HF/6-31+G,3-21G levels of theory, and the energetics of these modes of coordination have been calculated with the inclusion of electron correlation by the MP2 and MP4 methods. The bidentate and tridentate structures for BF{sub 4}{sup {minus}}Li{sup +} have been studied at various levels of calculation up to MP2/6-311+G*//MP2/6-31G*. Vibrational frequencies, {sup 10}B isotope frequency shifts, and infrared intensities have been calculated at the HF/3-21G level for each ion pair and at the HF/6-31+G,3-21G level for the tridentate BF{sub 4}{sup {minus}}K{sup +} ion pair. The tridentate structure is preferred for Na{sup +}, K{sup +}, and Rb{sup +}, but the bidentate structure is preferred for Li{sup +}. The topological, structural, energetic, and spectral consequences of the changing nature of the cation in the ion pairs are discussed.

• OSTI ID: 6081147
• Journal Information: Journal of Physical Chemistry; (USA), Journal Name: Journal of Physical Chemistry; (USA) Vol. 94:23; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

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