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Spectroscopic Evidence for Clusters of Like-Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding.

ABSTRACT: Direct spectroscopic evidence for hydrogen-bonded clusters of like-charged ions is reported for ionic liquids. The measured infrared O-H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion-corrected DFT calculated frequencies of linear and cyclic clusters. Compensating the like-charge Coulomb repulsion, these cationic clusters can range up to cyclic tetramers resembling molecular clusters of water and alcohols. These ionic clusters are mainly present at low temperature and show strong cooperative effects in hydrogen bonding. DFT-D3 calculations of the pure multiply charged clusters suggest that the attractive hydrogen bonds can compete with repulsive Coulomb forces.

SUBMITTER: Knorr A

PROVIDER: S-EPMC4819523 | biostudies-literature | 2016 Feb

REPOSITORIES: biostudies-literature

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Spectroscopic Evidence for Clusters of Like-Charged Ions in Ionic Liquids Stabilized by Cooperative Hydrogen Bonding.

Knorr Anne A Stange Peter P Fumino Koichi K Weinhold Frank F Ludwig Ralf R

Chemphyschem : a European journal of chemical physics and physical chemistry 20160108 4

Direct spectroscopic evidence for hydrogen-bonded clusters of like-charged ions is reported for ionic liquids. The measured infrared O-H vibrational bands of the hydroxyethyl groups in the cations can be assigned to the dispersion-corrected DFT calculated frequencies of linear and cyclic clusters. Compensating the like-charge Coulomb repulsion, these cationic clusters can range up to cyclic tetramers resembling molecular clusters of water and alcohols. These ionic clusters are mainly present at ...[more]

PMID: 26670942

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