<> "The repository administrator has not yet configured an RDF license."^^ . <> . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS"^^ . "In this work, two-dimensional infrared (2D-IR) spectroscopy investigates the timescale of solvent fluctuations for proton and hydride transfers. To elucidate hydride transfer dynamics, the BH stretch of \\ce{BH4-} is probed in various solvents from \\ce{H2O} to ionic liquids (ILs). For proton transfer dynamics, a vibrational probe (\\ce{SCN-}) explores the three-dimensional hydrogen bonding environment of a protic ionic liquid (PIL). \r\n \r\n\\ce{BH4-} is first investigated in increasing NaOH concentrations to develop a molecular understanding of suppressing the hydrogen evolution reaction. As the concentration increases, the timescale of frequency fluctuations decrease. Born Oppenheimer molecular dynamics (BOMD) simulations suggest that a crowding effect of ions around \\ce{BH4-} inhibits the rearrangement of dihydrogen bonds between \\ce{BH4-} and \\ce{H2O}. To completely suppress the hydrogen evolution reaction, ILs with \\ce{BH4-} as the anion are investigated. The linear and 2D-IR spectra of the antisymmetric BH stretch of \\ce{BH4-} are complicated due to Fermi resonances. The narrow linear and 2D-IR linewidths of \\ce{BH4-} in an IL allow a comprehensive assignment of all diagonal peaks and crosspeaks. Confirmed with a model Hamiltonian, two anharmonicities for the antisymmetric BH stretch of \\ce{BH4-} are characterized. \r\n\r\nPolarization- and temperature-dependent 2D-IR is employed to investigate the hydrogen bonding network of the PIL ethyl-ammonium nitrate (EAN). \\ce{SCN-} experiences two hydrogen bonding subensembles in EAN as two separate vibrational relaxation times are resolved. Furthermore, the polarization-weighted frequency fluctuation correlation function can be separated into two components: structural spectral diffusion (SSD) and reorientation-induced spectral diffusion (RISD). For \\ce{SCN-} in EAN, the timescales of frequency fluctuations are in the rotational limit as the SSD is unresolved. Temperature-dependent 2D-IR extracts the enthalpy and entropy of activation for frequency fluctuations. For \\ce{SCN-} in EAN, the enthalpy of activation for rotational motions are similar as to \\ce{SCN-} in \\ce{H2O}, and this suggests that the breaking and forming of hydrogen bonds around \\ce{SCN-} undergoes a similar mechanism in EAN as in \\ce{H2O}."^^ . "2020-09-16" . . . . . . . . "Clinton"^^ . "Johnson"^^ . "Clinton Johnson"^^ . . . . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (PDF)"^^ . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (Other)"^^ . . . . . . "lightbox.jpg"^^ . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (Other)"^^ . . . . . . "preview.jpg"^^ . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (Other)"^^ . . . . . . "medium.jpg"^^ . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (Other)"^^ . . . . . . "small.jpg"^^ . . . "USING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS (Other)"^^ . . . . . . "indexcodes.txt"^^ . . "HTML Summary of #39494 \n\nUSING ULTRAFAST VIBRATIONAL SPECTROSCOPY FOR A COMPREHENSIVE UNDERSTANDING OF STRUCTURAL AND ROTATIONAL MOTIONS FOR WATER TO PROTIC IONIC LIQUIDS\n\n" . "text/html" . .