title: Nonresonant and resonant mode-specific intermolecular vibrational energy transfers in electrolyte aqueous solutions.
abstract: The donor/acceptor energy mismatch and vibrational coupling strength dependences of interionic vibrational energy transfer kinetics in electrolyte aqueous solutions were investigated with ultrafast multiple-dimensional vibrational spectroscopy. An analytical equation derived from the Fermi's Golden rule that correlates molecular structural parameters and vibrational energy transfer kinetics was found to be able to describe the intermolecular mode specific vibrational energy transfer. Under the assumption of the dipole-dipole approximation, the distance between anions in the aqueous solutions was obtained from the vibrational energy transfer measurements, confirmed with measurements on the corresponding crystalline samples. The result demonstrates that the mode-specific vibrational energy transfer method holds promise as an angstrom molecular ruler.
authors.affiliation: Department of Chemistry, Rice University, Houston, Texas 77005, United States.
authors.forename: Hongtao
authors.initials: H
authors.lastname: Bian
authors.forename: Hailong
authors.initials: H
authors.lastname: Chen
authors.forename: Jiebo
authors.initials: J
authors.lastname: Li
authors.forename: Xiewen
authors.initials: X
authors.lastname: Wen
authors.forename: Junrong
authors.initials: J
authors.lastname: Zheng
mesh_terms: D000838:Anions; D002627:Chemistry, Physical; D003460:Crystallization; D004573:Electrolytes / Q000737:chemistry*; D004735:Energy Transfer; D007700:Kinetics; D008958:Models, Molecular; D012996:Solutions; D017550:Spectroscopy, Fourier Transform Infrared; D013816:Thermodynamics; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D000838:Anions; D004573:Electrolytes; D012996:Solutions; D014867:Water