Microscopic structure and dynamics of air/water interface by computer simulations—comparison with sum-frequency generation experiments

Wang, Yanting; Hodas, Nathan O.; Jung, Yousung; Marcus, R. A.

doi:10.1039/c0cp02745f

Cited by 14 publications

(12 citation statements)

References 44 publications

(87 reference statements)

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“…The same type of phenomenon has been proposed to account for the high reactivity of other species that are stabilized in the water lattice when presented at defects (interfaces) in that lattice. [53] Strong acid (HX) therefore has the counterintuitive effect of enhancing the utility of fluoride as a nucleophile, but not as a base, by generating a form of the anion (bifluoride) that can be presented more effectively at water interfaces. [54] Examples of sulfonyl fluorides made from the corresponding chlorides in this way are shown in Figure 5.…”

Section: Synthesis Of Sulfonyl Fluorides From Chloridesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

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Section: Synthesis Of Sulfonyl Fluorides From Chloridesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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“…To find this ensemble, one needs to define the geometrical criteria. 178 The O−H group defined by the optimized free O−H group criterion should include the whole 3700 cm −1 positive SFG feature and exclude the negative SFG feature in the frequency region of ω ≤ 3600 cm −1 . Furthermore, the free O−H groups captured by this criterion should reproduce (1) the experimentally obtained orientational parameter, d ≡ ⟨cos Ω⟩/ ⟨cos 3 Ω⟩ of 1.55 ± 0.02, 179 and (2) the free O−H group lifetime of 1.1 ps.…”

Section: Geometrical Conformation Of Free O−h Groupsmentioning

confidence: 99%

“…To find this ensemble, one needs to define the geometrical criteria . The O–H group defined by the optimized free O–H group criterion should include the whole 3700 cm –1 positive SFG feature and exclude the negative SFG feature in the frequency region of ω ≤ 3600 cm –1 .…”

Section: Simulation Frameworkmentioning

confidence: 99%

Molecular Structure and Modeling of Water–Air and Ice–Air Interfaces Monitored by Sum-Frequency Generation

et al. 2020

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From a glass of water to glaciers in Antarctica, water–air and ice–air interfaces are abundant on Earth. Molecular-level structure and dynamics at these interfaces are key for understanding many chemical/physical/atmospheric processes including the slipperiness of ice surfaces, the surface tension of water, and evaporation/sublimation of water. Sum-frequency generation (SFG) spectroscopy is a powerful tool to probe the molecular-level structure of these interfaces because SFG can specifically probe the topmost interfacial water molecules separately from the bulk and is sensitive to molecular conformation. Nevertheless, experimental SFG has several limitations. For example, SFG cannot provide information on the depth of the interface and how the orientation of the molecules varies with distance from the surface. By combining the SFG spectroscopy with simulation techniques, one can directly compare the experimental data with the simulated SFG spectra, allowing us to unveil the molecular-level structure of water–air and ice–air interfaces. Here, we present an overview of the different simulation protocols available for SFG spectra calculations. We systematically compare the SFG spectra computed with different approaches, revealing the advantages and disadvantages of the different methods. Furthermore, we account for the findings through combined SFG experiments and simulations and provide future challenges for SFG experiments and simulations at different aqueous interfaces.

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“…47) and 27% (Ref. 84) from molecular dynamics simulations using HB definitions that are less restrictive than those conventionally used but still containing arbitrary parameters. Equivalently, all these values translate to 10%-14% broken HBs, assuming one broken HB per water molecule.…”

Section: Acceptormentioning

confidence: 99%

Long-range hydrogen-bond structure in aqueous solutions and the vapor-water interface

Irudayam

Henchman

2012

The Journal of Chemical Physics

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There is a considerable disagreement about the extent to which solutes perturb water structure. On the one hand, studies that analyse structure directly only show local structuring in a solute's first and possibly second hydration shells. On the other hand, thermodynamic and kinetic data imply indirectly that structuring occurs much further away. Here, the hydrogen-bond structure of water around halide anions, alkali cations, noble-gas solutes, and at the vapor-water interface is examined using molecular dynamics simulations. In addition to the expected perturbation in the first hydration shell, deviations from bulk behavior are observed at longer range in the rest of the simulation box. In particular, at the longer range, there is an excess of acceptors around halide anions, an excess of donors around alkali cations, weakly enhanced tetrahedrality and an oscillating excess and deficiency of donors and acceptors around noble-gas solutes, and enhanced tetrahedrality at the vapor-water interface. The structuring compensates for the short-range perturbation in water-water hydrogen bonds induced by the solute. Rather than being confined close to the solute, it is spread over as many water molecules as possible, presumably to minimize the perturbation to each water molecule.

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Microscopic structure and dynamics of air/water interface by computer simulations—comparison with sum-frequency generation experiments

Cited by 14 publications

References 44 publications

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Molecular Structure and Modeling of Water–Air and Ice–Air Interfaces Monitored by Sum-Frequency Generation

Long-range hydrogen-bond structure in aqueous solutions and the vapor-water interface

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