Two-Dimensional IR Spectroscopy as a Window into the Molecular Structure and Dynamics of Electrolytes and Ionic Liquids: A Review
- 1Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, United States
Abstract
Two-dimensional infrared (2DIR) spectroscopy has emerged as a powerful tool for probing the structure and picosecond dynamics of complex, condensed-phase systems at the molecular level. In electrolytes and ionic liquids, where physicochemical properties arise from the interplay between solvation and ionic interactions, 2DIR spectroscopy provides unique insights into intermolecular interactions and dynamical processes that are often inaccessible to conventional spectroscopies. This review highlights seminal and recent advances in understanding the behavior of these systems using 2DIR spectroscopy, with particular emphasis on spectral diffusion, vibrational relaxation, and chemical exchange dynamics. The review also describes how complementary information from the vibrational modes of solvents, salts, and external probes enables detailed characterization of ion–ion interactions, hydrogen-bonding networks, and solvation environments, providing a molecular framework of the structure and time evolution of these charged systems. Moreover, particular attention is given to the dynamics of distinct molecular moieties and to the role of specific anions, cations, and solvent environments in governing behavior on femtosecond to picosecond time scales. Finally, the review describes current challenges, including the limited availability of intrinsic vibrational reporters and experimental constraints, and key open questions in electrochemical and energy-relevant systems that remain despite an extensive number of studies in the area.
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BibTeX
@article{bonilla2026twodimensional,
title = {{Two-Dimensional IR Spectroscopy as a Window into the Molecular Structure and Dynamics of Electrolytes and Ionic Liquids: A Review}},
author = {Valeria Bonilla and Daniel G. Kuroda},
journal = {Chemical Reviews},
year = {2026},
month = oct,
doi = {10.1021/acs.chemrev.6c00440},
url = {https://doi.org/10.1021/acs.chemrev.6c00440},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Two-Dimensional IR Spectroscopy as a Window into the Molecular Structure and Dynamics of Electrolytes and Ionic Liquids: A Review
AU - Valeria Bonilla
AU - Daniel G. Kuroda
PY - 2026
DA - 2026/10/14
JO - Chemical Reviews
DO - 10.1021/acs.chemrev.6c00440
UR - https://doi.org/10.1021/acs.chemrev.6c00440
AB - Two-dimensional infrared (2DIR) spectroscopy has emerged as a powerful tool for probing the structure and picosecond dynamics of complex, condensed-phase systems at the molecular level. In electrolytes and ionic liquids, where physicochemical properties arise from the interplay between solvation and ionic interactions, 2DIR spectroscopy provides unique insights into intermolecular interactions and dynamical processes that are often inaccessible to conventional spectroscopies. This review highlights seminal and recent advances in understanding the behavior of these systems using 2DIR spectroscopy, with particular emphasis on spectral diffusion, vibrational relaxation, and chemical exchange dynamics. The review also describes how complementary information from the vibrational modes of solvents, salts, and external probes enables detailed characterization of ion–ion interactions, hydrogen-bonding networks, and solvation environments, providing a molecular framework of the structure and time evolution of these charged systems. Moreover, particular attention is given to the dynamics of distinct molecular moieties and to the role of specific anions, cations, and solvent environments in governing behavior on femtosecond to picosecond time scales. Finally, the review describes current challenges, including the limited availability of intrinsic vibrational reporters and experimental constraints, and key open questions in electrochemical and energy-relevant systems that remain despite an extensive number of studies in the area.
SN - 0009-2665
SN - 1520-6890
ER -