Ab Initio Model Study of the Mechanism of Chlorine Nitrate Hydrolysis on Ice

Bianco, Roberto; Hynes, James T.

doi:10.1021/jp970466c

Cited by 84 publications

(181 citation statements)

References 39 publications

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“…Vincent et al 64 elucidated the mechanism of oxidation of SO 2 by H 2 O 2 in water droplets, whereas Smith et al 65 examined the process of acid dissociation in water clusters. Our recent calculations concerning the hydrolysis of ClONO 2 , 52,53 in addition to the work of Bianco and Hynes, 49 have shown these prototypical clusters to suitably reproduce the observed reactivity of the PSC surface and small water droplets. Models that represent the local adsorption site by fragments excised from an ideal ice lattice 58,60 may not account for the solvating effect of the ice surface beyond the adsorption site.…”

Section: Modeling Small Water Droplets and The Ice Surfacementioning

confidence: 69%

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

2000

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High-level electronic structure calculations were used to study the mechanism of the reaction of ClONO 2 with HCl in neutral water clusters containing one to five solvating water molecules. For the reaction between molecular HCl and ClONO 2 , the barrier decreases from 42 kcal mol -1 (uncatalyzed) to essentially zero when catalyzed by only two water molecules, where the reaction products involve Cl 2 and HONO 2 . The calculations thus predict that the gas-phase reaction may be important in the stratospheric reactivation of ClONO 2 . The reaction between ClONO 2 and solvated H 3 O + Cl -, as on the polar stratospheric cloud (PSC) surface, was investigated with clusters involving up to seven water molecules. The ice-catalyzed reaction involves an ionic mechanism whereby charge transfer to ClONO 2 from the attacking nucleophile leads to significant ionization along the Cl-ONO 2 bond. The effect of the size of the first solvation shell of Cl -is addressed by our calculations. In a cluster containing three waters and a five-water cluster structurally related to hexagonal ice, ClONO 2 reacts spontaneously with HCl to yield Cl 2 /HONO 2 in the three-water reaction and Cl 2 /H 3 O + -NO 3 -in the five-water-catalyzed reaction. The calculations thus predict that the reaction of ClONO 2 with HCl on PSC ice aerosols can proceed spontaneously via an ionic pathway.

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Section: Modeling Small Water Droplets and The Ice Surfacementioning

confidence: 69%

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

2000

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“…The fact that the yield decreases as increasing methane concentration may exclude the possibility of a methane cluster ion. In addition, the close resemblance between the contour pattern of 31 amu species and that of 3 CH + suggests the same mother cluster for both species, namely (CH 4 ) 1-2 (H 2 O) [1][2] . From these observation, this species likely to be CH 3 O + , which is synthesized in the water-methane heterocluster.…”

Section: Water and Methane Coadsorbed On Solid Nementioning

confidence: 86%

“…The role of the ice surface as a stage of chemical reaction has been studied in the wide variety of fields such as interstellar astrophysics [1], atomospheric science [2,3], and biological science. Specifically in the interstellar astrophysics [4], it is considered that the ice surface of the interstellar dust provides the stage where a complex organic molecule is synthesized from simple molecules.…”

Section: Introductionmentioning

confidence: 99%

Photo-stimulated desorption from water and methane clusters on the surface of solid neon

Arakawa

Matsumoto

Takekuma

et al. 2012

Low Temperature Physics

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Photo-stimulated desorption of ions from methane and water heterocluster on the surface of solid neon was studied. The desorption yields of the variety of photo-desorbed species showed strong dependence on the composition and the size of the mother cluster. It was found that the presence of a water molecule in the cluster significantly enhanced, or was almost essential for, the desorption of any species observed. Systematic investigation of the correlation between the cluster size and the desorption yield of each ion has revealed the mother cluster which yields the each desorbed ion.

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“…As for the net Cl 2 -producing reaction itself, one suggestion was that it occurred in two steps, the first being the hydrolysis of chlorine nitrate, ClONO 2 + H 2 O → HOCl + HNO 3 , followed by HCl+ HOCl → H 2 O + Cl 2 . Postdoc Roberto Bianco and I found the hydrolysis on a model of ice to be quite facile, courtesy of a proton relay chain (PRC) that assisted both water's nucleophilic attack on ClONO 2 's (electropositive) Cl atom and the stabilization of the NO − 3 leaving group (139). But later evidence suggested that the single-step mechanism cited above was in fact more likely, and indeed, our examination of the HCl + ClONO 2 reaction on modeled ice showed this reaction to also be facile, with once again crucial PRC assistance (140).…”

Section: Atmospheric Interstellar Biological and Renewable Energy mentioning

confidence: 99%

Molecules in Motion: Chemical Reaction and Allied Dynamics in Solution and Elsewhere

Hynes

2015

Annu. Rev. Phys. Chem.

Self Cite

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After my acceptance of the kind invitation from Todd Martínez and Mark Johnson, Co-Editors of this journal, to write this article, I had to decide just how to actually do this, given the existence of a fairly personal and extended autobiographical account of recent vintage detailing my youth, education, and assorted experiences and activities at the University of Colorado, Boulder, and later also at Ecole Normale Supérieure in Paris (1). In the end, I settled on a differently styled recounting of the adventures with my students, postdocs, collaborators, and colleagues in trying to unravel, comprehend, describe, and occasionally even predict the manifestations and consequences of the myriad assortment of molecular dances that contribute to and govern the rates and mechanisms of chemical reactions in solution (and elsewhere TRANSLATIONAL, ROTATIONAL, AND SOLVATION DYNAMICS IN SOLUTIONThis is basically where it all began for me. Beyond their fundamental interest, these three types of dynamics (translational, rotational, and solvation) can be important for chemical reactions in assorted regimes, although admittedly this is perhaps not always so obvious: Translation is relevant for diffusion-controlled and -influenced reactions, water rotation is important for proton transfers (PTs), for example, and solvation dynamics can have a significant effect on any reaction involving the redistribution or rearrangement of charges. I give only brief commentaries on our work at the University of Colorado, Boulder, on these types of dynamics in the 1970s and 1980s and end with more recent aspects carried out at Ecole Normal Supérieure (ENS).In the 1970s, it was thought by not a few that macroscopic continuum hydrodynamics-as reflected in, e.g., Stokes' friction laws for translation and rotation, the Stokes-Einstein equation for translational diffusion, and the Debye-Stokes-Einstein relation for rotational or reorientational diffusion-could actually apply in detail, and even quantitatively, at a molecular level. I myself have used (and continue to use) continuum hydrodynamic and dielectric models to provide concepts, perspectives, and guides for experiment. Clearly, I like such models greatly, but I just could not accept going this far. Together with Mike Weinberg and Ray Kapral (2-4), we addressed the issue with what we called a microscopic boundary layer approach, combining a molecular collisional picture for the immediate solvent neighborhood of a rotating or translating solute molecule with a hydrodynamic description of the remaining, outer solvent. We showed that for both rotational and translational friction (and thus for diffusion), the molecular aspects were indeed dominant. Although hydrodynamic influences could also enter, they only became the dominant story when the solute was far larger than the solvent molecules. We also found that the supposed agreement of assorted simulations and experiments with the hydrodynamic view disappeared upon suitable scrutiny. Solvation DynamicsThis flavor of dynamics came into it...

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Ab Initio Model Study of the Mechanism of Chlorine Nitrate Hydrolysis on Ice

Cited by 84 publications

References 39 publications

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

Photo-stimulated desorption from water and methane clusters on the surface of solid neon

Molecules in Motion: Chemical Reaction and Allied Dynamics in Solution and Elsewhere

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Ab Initio Model Study of the Mechanism of Chlorine Nitrate Hydrolysis on Ice

Cited by 84 publications

References 39 publications

Exploration of the Mechanism of the Activation of ClONO2by HCl in Small Water Clusters Using Electronic Structure Methods

Exploration of the Mechanism of the Activation of ClONO2by HCl in Small Water Clusters Using Electronic Structure Methods

Photo-stimulated desorption from water and methane clusters on the surface of solid neon

Molecules in Motion: Chemical Reaction and Allied Dynamics in Solution and Elsewhere

Contact Info

Product

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Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods

Exploration of the Mechanism of the Activation of ClONO₂by HCl in Small Water Clusters Using Electronic Structure Methods