Molecular Dynamics Simulation of the Concentration Effect on the Structure and Physicochemical Properties of Lithium Perchlorate Solutions in Sulfolane
Russian Journal of Physical Chemistry A, cilt.96, sa.5, ss.993-1003, 2022 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 96 Sayı: 5
- Basım Tarihi: 2022
- Doi Numarası: 10.1134/s003602442205017x
- Dergi Adı: Russian Journal of Physical Chemistry A
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Aquatic Science & Fisheries Abstracts (ASFA), Compendex
- Sayfa Sayıları: ss.993-1003
- Anahtar Kelimeler: coordination number, lithium perchlorate, molecular dynamics, radial distribution function, solvation shell, sulfolane
- Boğaziçi Üniversitesi Adresli: Evet
Özet
Abstract: Molecular dynamics simulation of LiClO4 solutions in sulfolane has been performed in a wide range of concentrations from 2 × 102 to 7 × 103 mol/m3 (7 M) using the Opslaa force field. It was found that the total coordination number (the sum of coordination numbers for sulfolane and perchlorate anion) of the lithium cation decreased with an increase in the lithium perchlorate concentration in solution from 5.7 to 4.5. It was shown that sulfolane solvates one lithium cation by one oxygen atom regardless of the salt concentration; but above the salt concentration 2 × 103 mol/m3 (2 M) (molar ratio of sulfolane/LiClO4 < 5), sulfolane acts as a bridging ligand between two lithium cations; the lithium perchlorate anion is coordinated with the lithium cation by one oxygen atom; only at the molar ratio sulfolane/LiClO4 = 1 (salt concentration 7 × 103 mol/m3) the perchlorate anion acts as a bridging ligand and is coordinated with several lithium cations at once. At a concentration of 2.35 × 103 mol/m3 (sulfolane/LiClO4 = 4), the structure of the first solvation shell of the lithium cation changes; the perchlorate anion is introduced in it, filling the vacancies in the coordination sphere that appear because of the lack of free sulfolane molecules.