Showing papers by "Richard J. Saykally published in 2015"
TL;DR: In this paper, a detailed chronological review of the experimental studies and insights into the complex nature of water and hydrogen bonding gained from them is presented, and a subsequent letter will review the corresponding theoretical advances.
118 citations
TL;DR: The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.
Abstract: Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study. In this work, we describe the study of aqueous solutions of sodium nitrate and nitrite via X-ray absorption spectroscopy (XAS), interpreted in light of first-principles density functional theory electronic structure calculations. Experimental and calculated spectra of the nitrogen K-edge XA spectra of bulk solutions exhibit a large 3.7 eV shift between the XA spectra of nitrate and nitrite resulting from greater stabilization of the nitrogen 1s energy level in nitrate. A similar shift is not observed in the oxygen K-edge XA spectra of NO3 (-) and NO2 (-). The hydration properties of nitrate and nitrite are found to be similar, with both anions exhibiting a similar propensity towards ion pairing.
32 citations
TL;DR: Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.
Abstract: We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm(-1) and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is ~524 cm(-1). Librational excitation increases the interchange and bifurcation hydrogen bond rearrangement tunneling splittings by factors of 3-5 and 4-40, respectively. Analysis of the rotational constants obtained from a nonlinear least squares fit indicates that additional external perturbations to the energy levels are likely.
28 citations
TL;DR: In this paper, the authors report the detailed characterization of dissolved CO2 gas through the combination of X-ray spectroscopy and first principles theory, showing that CO2 acts as a hydrophobe in water with an average hydrogen bond number of 0.56.
14 citations
TL;DR: In this paper, the first application of a commercial Terahertz quantum cascade laser (QCL) system for high resolution spectroscopy of supersonic beams is presented, where the QCLs exhibited continuous linear voltage tuning over a 2GHz range about a center frequency of 3.762
7 citations
DOI•
01 Jan 2015
TL;DR: In this article, Otten et al. used second-harmonic generation spectroscopy (SHG) for measuring the strong charge transfer to solvent (CTTS) transitions characteristic of all stable aqueous anions.
Abstract: Author(s): Otten, DE; Saykally, RJ | Abstract: The development of deep-UV second-harmonic generation spectroscopy (SHG) for measuring the strong charge transfer to solvent (CTTS) transitions characteristic of all stable aqueous anions has provided a powerful new probe of water interfaces. By employing suitable models, quantitative thermodynamic results have been obtained for a number of fundamental electrolytes, which are generally in good agreement with theoretical calculations. Details of the experiments and models are described and salient results supporting a novel mechanism for the selective adsorption of ions to the air/water interface are reviewed.
1 citations