Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 118, Issue 13, Pages 3689-3695Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp500877u
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Funding
- National Natural Science Foundation of China [21373213]
- Chinese Academy of Sciences
- Ministry of Science and Technology
- Welch foundation [C-1752]
- Air Force Office of Scientific Research under AFOSR Award [FA9550-11-1-0070]
- David and Lucile Packard Foundation
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The coordination number of Li+ in acetonitrile solutions was determined by directly measuring the rotational times of solvent molecules bound and unbound to it. The CN stretch of the Li+ bound and unbound acetonitrile molecules in the same solution has distinct vibrational frequencies (2276 cm(-1) vs 2254 cm(-1)). The frequency difference allows the rotation of each type of acetonitrile molecule to be determined by monitoring the anisotropy decay of each CN stretch vibrational excitation signal. Regardless of the nature of anions and concentrations, the Li+ coordination number was found to be 4-6 in the LiBF4 (0.2-2 M) and LiPF6 (1-2 M) acetonitrile solutions. However, the dissociation constants of the salt are dependent on the nature of anions. In 1 M LiBF4 solution, 53% of the salt was found to dissociate into Lit, which is bound by 4-6 solvent molecules. In 1 M LiPF6 solution, 72% of the salt dissociates. 2D IR experiments show that the binding between Li+ and acetonitrile is very strong. The lifetime of the complex is much longer than 19 ps.
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