Hydrogen bond and cooperative effect in the reactions of HOCl with HCl on water clusters

Xu, Si Chuan

doi:10.1063/1.479565

Cited by 29 publications

(17 citation statements)

References 36 publications

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“… Equations 30 and 31 comprise a two-step mechanism, whereas eq 32 is a single step to form the active Cl 2 (g) product. , Upon examination of the aforementioned mechanisms, it becomes clear that the role of the interaction of HCl with the PSC provides a common denominator. Thus, there have been numerous experimental and theoretical studies designed to understand the uptake of HCl and its concomitant chemistry. ,,− Measurements have characterized the uptake of HCl on well-characterized ice films (prototypical type II PSCs) with results ranging from 2 × 10 13 to 4 × 10 14 molecules/cm 2 under conditions approaching ...…”

Section: Solid−vapor Interfacesmentioning

confidence: 99%

First-Principles Approaches to the Structure and Reactivity of Atmospherically Relevant Aqueous Interfaces

Mundy

Kuo

2006

Chem. Rev.

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Section: Solid−vapor Interfacesmentioning

confidence: 99%

First-Principles Approaches to the Structure and Reactivity of Atmospherically Relevant Aqueous Interfaces

Mundy

Kuo

2006

Chem. Rev.

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“…In the real ice crystal the isomers are considered as distributed with equal (or almost equal) probabilities and the properties of ice are considered as average values of all the possible isomers. During the computational studies of ice or ice surfaces, the cluster models (see for example [12][13][14][15][16][17] and numerous references therein) propose that only one or several possible orientational isomers of the cluster have to be considered. Most frequently, the random choice of the hydrogen bond network is used.…”

Section: Introductionmentioning

confidence: 99%

H2O2 adsorption on the ice Ih surface. Theoretical study with systematic assessment of the orientation isomerism of the hydrogen bond network

Ignatov

Разуваев

Сенников

et al. 2009

Journal of Molecular Structure: THEOCHEM

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a b s t r a c tSemiempirical (PM3) and DFT (B3LYP/6-31++G(d,p)) calculations of the structure and energies of the variety of water clusters modeling 4680 fragments of the ice surface with different topology of the hydrogen bond network have been performed in order to analyze the contributions of various orientational isomers into the energy distributions of clusters and their impact onto the adsorption ability relatively to the H 2 O 2 molecule. It was found that, in the framework of the considered model, only several kinds of surface patterns among all the possible structures have significant thermodynamic weights and, thus, have the maximum contributions into the adsorption energy. Structural and energetic properties of the adsorption complexes formed by H 2 O 2 molecule with the most favourable fragments of the ice surface are analyzed on the basis of B3LYP/6-311++G(2d,2p) calculations.

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“…To facilitate the proton transfer, the loosening of the O-H bond should be concerted to cooperate with formation of the N-H bond, similar to what was found in previous works [64][65][66]. The reason is that movement of a lone electron pair and proton is characterized with directionality along a strong hydrogen bond.…”

Section: Figurementioning

confidence: 60%

The tautomerization of H2NCH2C(OH)NH to H2NCH2CONH2 in the interstellar medium

Deng

et al. 2010

Sci. China Phys. Mech. Astron.

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The tautomerization of H 2 NCH 2 C(OH)NH to H 2 NCH 2 CONH 2 is an important step by way of Strecker synthesis for the production of glycine in the interstellar medium (ISM) with respect to the origin of amino acids on the early Earth. Our work indicates two mechanisms for the tautomerization to occur. k CVT/SCT (rate constant) is 45.6 s −1 at 50 K, obtained with the small curvature tunneling (SCT) approximation and canonical variational transition state theory (CVT), to support one mechanism assisted by quantum tunneling in the ISM. Another mechanism is through the (H 2 O) 2 -coupled proton transfer. In the (H 2 O) 2 -coupled reaction, two H 2 O molecules act as a catalyst to reduce the barrier energy by 23.7 kcal mol −1 , and cooperatively let a proton pass a hydrogen-bonded bridge composed of H 2 NCH 2 C(OH)NH with (H 2 O) 2 . k TST is 8.08×10 −4 s −1 at 100 K, calculated with TST kinetics, to demonstrate the mechanism. Therefore, the tautomerization is feasible in the ISM. H 2 NCH 2 C(OH)NH and H 2 NCH 2 CONH 2 will be detected in the ISM and found in carbonaceous chondrites. The results present new evidence for the third theory on the origin of amino acids on the early Earth.

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Hydrogen bond and cooperative effect in the reactions of HOCl with HCl on water clusters

Abstract: Direct ab initio dynamics calculations for rates and the kinetic isotope effects of multiproton transfer in ClONO 2 + HCl → HNO 3 + Cl 2 reactions with water clusters: Breakdown of the rule of the geometric mean

Cited by 29 publications

References 36 publications

First-Principles Approaches to the Structure and Reactivity of Atmospherically Relevant Aqueous Interfaces

First-Principles Approaches to the Structure and Reactivity of Atmospherically Relevant Aqueous Interfaces

H2O2 adsorption on the ice Ih surface. Theoretical study with systematic assessment of the orientation isomerism of the hydrogen bond network

The tautomerization of H2NCH2C(OH)NH to H2NCH2CONH2 in the interstellar medium

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