Electric Field Reversal of Na2SO4, (NH4)2SO4, and Na2CO3 Relative to CaCl2 and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency

Wei, Hua; Jubb, Aaron M.; Allen, Heather C.

doi:10.1021/jz200888t

Cited by 67 publications

(133 citation statements)

References 57 publications

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“…The 1.1 M solution was specifically chosen to facilitate comparison with the SFG spectroscopy results of Allen and coworkers on the air-water interface structure of aqueous Na 2 CO 3 . 23 The solutions pH were 12.1…”

Section: Experimental Methodsmentioning

confidence: 99%

“…23 Miller and coworkers used a combination of SFG spectroscopy and MD simulations to show (a) that both the carbonate and sodium ions are excluded at a large distance from the air-water interface (>10 Å), and (b) that this exclusion creates a more polar-ordered hydrogen bonding network and a broader interface. 31 However, to which degree these ion distributions and water reorientation extends into the solution is not known from SFG measurements alone.…”

Section: Ion Spatial Distributions In Vacuum-aqueous Electrolyte Intementioning

confidence: 99%

“…However, before model predictions can be generalized the input parameters and assumptions must be validated by analytical measurements that can provide molecular level insight at the water interface. In this regard, three prominent analytical techniques have recently proved noteworthy complements to the well established macroscopic techniques of surface tension [8][9] and surface potential [10][11] for the study of air (vacuum)-water interfaces: second harmonic generation (SHG), [12][13][14][15][16][17][18][19][20][21][22] sum-frequency generation (SFG) spectroscopy [23][24][25][26][27][28][29][30][31] and liquid based X-ray photoelectron spectroscopy (XPS). [32][33][34][35][36][37][38][39][40][41][42][43][44][45] All three of these methods are capable of interrogating the microscopic structure of the air (vacuum)-water interface, and often provide complementary information due to the different properties probed.…”

Section: Introductionmentioning

confidence: 99%

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Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces

et al. 2015

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The spatial distribution of electrolyte ions at water interfaces remains a topic of considerable interest to the atmospheric, geochemical and physical sciences communities. Here, the depthresolved spatial distributions of K + and CO 3 2− from 0.5 M and 1.1 M aqueous solutions of potassium carbonate (K 2 CO 3 ) are measured by synchrotron based X-ray photoelectron spectroscopy (XPS) in combination with a liquid microjet. The ion distributions determined from the intensities of the K 2p and C 1s orbitals are consistent with the K + cation residing on average slightly closer to the interface than the CO 3 2− anion. The interface of this solution is the broadest yet reported for an electrolyte solution by depth-resolved XPS, consistent with earlier molecular dynamics simulations of aqueous Na 2 CO 3 that showed a large (>1 nm) ion depletion layer at the interface. Results are compared, where possible, between liquid jets running in vacuum (1 × 10 −4 mbar) and jets in an equilibrated background vapor pressure that is determined by the temperature of the solution (6 mbar in this case). The ion spatial distributions and the molecular level pictures of the air-and vacuum-aqueous electrolyte interfaces as derived by XPS are identical.

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Section: Experimental Methodsmentioning

confidence: 99%

Section: Ion Spatial Distributions In Vacuum-aqueous Electrolyte Intementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces

et al. 2015

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“…[83][84][85][86] The differential Imχ (2) S spectra for different salts with respect to that of neat water are presented in Fig. 12.…”

Section: Studies Of Ion Adsorption At Water/air Interfacesmentioning

confidence: 99%

Study of Water Interfaces With Phase-Sensitive Sum Frequency Vibrational Spectroscopy

Tian¹

2014

Advances in Multi-Photon Processes and Spectroscopy

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Water interfaces are ubiquitous in the world. They play a crucial role in many physical, chemical, and biological systems. However, because very few experimental techniques are available for probing water/interfaces, the understanding at the molecular level of their physical and chemical properties is still poor. Sum frequency vibrational spectroscopy (SFVS) is so far the only technique that is capable of providing vibrational spectra of water surface/interface. It is applicable to study the structure of bare surface and buried interface with sub-monolayer sensitivity. The newly developed phase-sensitive SFVS technique provides Imχ(2) S (ω IR ) spectrum directly from experiment, with χ (2) S (ω IR ) being the second order susceptibility. The Imχ(2) S (ω IR ) spectrum obtained for the water interfaces allows much improved understanding of the water interfacial structure, in analogy to Imε, with ε being the dielectric constant, for the absorption or emission spectrum. This chapter covers recent advances in study of a few representative water interfaces, including water/air, water/hydrophobic material interfaces, with emphasis on phase-sensitive SFVS.

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“…[23][24][25][26] Vibrational spectroscopy is, in principle, an excellent method for probing H-bond interactions since the O-H stretch frequency is quite sensitive to the local environment. 27 Accordingly, there has been considerable effort directed at resolving resonances in the water spectrum, including isotope dilution, 28 interference measurements, [29][30][31][32][33][34][35] maximum entropy analysis, 36 vibrational dephasing, 37,38 hyperpolarizability orientation, 39 and modification of the surface via addition of salts. 34,[40][41][42] Important conclusions, specifically concerning the ion distribution and ionization state of acids and bases have emerged from these works.…”

Section: Introductionmentioning

confidence: 99%

Insights into hydrogen bonding via ice interfaces and isolated water

Shultz

Bisson

2014

The Journal of Chemical Physics

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Water in a confined environment has a combination of fewer available configurations and restricted mobility. Both affect the spectroscopic signature. In this work, the spectroscopic signature of water in confined environments is discussed in the context of competing models for condensed water: (1) as a system of intramolecular coupled molecules or (2) as a network with intermolecular dipole-dipole coupled O-H stretches. Two distinct environments are used: the confined asymmetric environment at the ice surface and the near-isolated environment of water in an infrared transparent matrix. Both the spectroscopy and the environment are described followed by a perspective discussion of implications for the two competing models. Despite being a small molecule, water is relatively complex; perhaps not surprisingly the results support a model that blends inter- and intramolecular coupling. The frequency, and therefore the hydrogen-bond strength, appears to be a function of donor-acceptor interaction and of longer-range dipole-dipole alignment in the hydrogen-bonded network. The O-H dipole direction depends on the local environment and reflects intramolecular O-H stretch coupling.

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Electric Field Reversal of Na₂SO₄, (NH₄)₂SO₄, and Na₂CO₃ Relative to CaCl₂ and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency

Cited by 67 publications

References 57 publications

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces

Study of Water Interfaces With Phase-Sensitive Sum Frequency Vibrational Spectroscopy

Insights into hydrogen bonding via ice interfaces and isolated water

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Electric Field Reversal of Na2SO4, (NH4)2SO4, and Na2CO3 Relative to CaCl2 and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency

Cited by 67 publications

References 57 publications

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K2CO3 Interfaces

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K2CO3 Interfaces

Study of Water Interfaces With Phase-Sensitive Sum Frequency Vibrational Spectroscopy

Insights into hydrogen bonding via ice interfaces and isolated water

Contact Info

Product

Resources

About

Electric Field Reversal of Na₂SO₄, (NH₄)₂SO₄, and Na₂CO₃ Relative to CaCl₂ and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces

Ion Spatial Distributions at the Air– and Vacuum–Aqueous K₂CO₃ Interfaces