The reaction of N2O5 with H3O+: A first‐principles direct molecular dynamics study of acid‐catalyzed reactive uptake of N2O5

Ishikawa, Sascha T.; Nakajima, Takahito

doi:10.1002/qua.22071

Cited by 4 publications

(3 citation statements)

References 24 publications

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“…The method was used to study the formation 12 and protonation of nitric acid, 13 as well as related systems; 14 photodetachment of an anion complex, (F À )(H 2 O) 4 , 15 S N 2 reactions; 16 unimolecular dissociation of H 2 CO and related molecules; 17,18 abstraction reactions of H atoms 19 and a few others. As the merits of MP2 in MD calculations became increasingly recognized, many more applications of the method were reported, including additional studies of nitric acid formation; [20][21][22][23][24] ionization dynamics (and the reverse process of electron capture); [25][26][27][28][29][30][31] S N 2 reactions; [32][33][34] dynamics in the transition state region, also in the context of unimolecular reactions; [35][36][37][38] hydrogen atom abstraction and elimination reactions [39][40][41][42][43][44] and a host of other processes. In the last several years, the use of MD-MP2 has become quite extensive, especially for polyatomic systems of small to moderate sizes.…”

Section: Direct Molecular Dynamics With Mp2 Potentials (Md-mp2)mentioning

confidence: 99%

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Gerber

Shemesh

Varner

et al. 2014

Phys. Chem. Chem. Phys.

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Recent progress in ''on-the-fly'' trajectory simulations of molecular reactions, using different electronic structure methods is discussed, with analysis of the insights that such calculations can provide and of the strengths and limitations of the algorithms available. New developments in the use of both ab initio and semi-empirical electronic structure algorithms are described. The emphasis is on: (i) calculations of electronic properties along the reactive trajectories and the unique insights this can contribute to the processes; (ii) electronic structure methods recently introduced to this topic to improve accuracy, extend applicability or enhance computational efficiency. The methods are presented with examples,including new results, of reactions of both isolated molecules and of molecules in media, mostly clusters. Possible future directions for this fast growing field are suggested.

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Section: Direct Molecular Dynamics With Mp2 Potentials (Md-mp2)mentioning

confidence: 99%

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Gerber

Shemesh

Varner

et al. 2014

Phys. Chem. Chem. Phys.

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“…Nitrogen oxides may participate in heterogeneous processes with condensed phases in the atmosphere, and here we focus specifically on interactions between nitrogen oxides and ice. Special attention has been given to dinitrogen pentoxide, N 2 O 5 , because of its prominent role in stratospheric ozone chemistry. − N 2 O 5 primarily forms by nitrogen dioxide reacting with ozone NO 2 + normalO 3 → NO 3 + normalO 2 followed by NO 3 + NO 2 .25em ( + M ) → normalN 2 normalO 5 .25em ( + M ) NO 3 is rapidly photolyzed by sunlight, and thus, the N 2 O 5 concentration reaches a maximum at night. N 2 O 5 may subsequently react to form nitric acid by either , normalN 2 normalO 5 ( g ) + normalH 2 normalO ( condensed ) → 2 HNO 3 ( condensed ) or normalN 2 normalO 5 ( g…”

Section: Introductionmentioning

confidence: 99%

“…Nitrogen oxides such as ClONO 2 function as chlorine reservoirs in the stratosphere, and therefore, denitrification results in reduced rates of chlorine removal, and consequently higher O 3 destruction rates . Reaction has been extensively studied on pure water ice, nitric acid hydrates, and surfaces containing H 2 SO 4 . − The reactive uptake coefficient for N 2 O 5 is observed to be higher on pure ice (0.024) than on nitric acid hydrates (0.0006) . Enhanced uptake coefficients have also been observed at sub-monolayer HNO 3 surface coverage, and the reaction has been suggested to be acid-catalyzed.…”

Section: Introductionmentioning

confidence: 99%

Interactions of N₂O₅ and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics

et al. 2014

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The detailed interactions of nitrogen oxides with ice are of fundamental interest and relevance for chemistry in cold regions of the atmosphere. Here, the interactions of NO, NO2, N2O4, and N2O5 with ice surfaces at temperatures between 93 and 180 K are investigated with molecular beam techniques. Surface collisions are observed to result in efficient transfer of kinetic energy and trapping of molecules on the ice surfaces. NO and NO2 rapidly desorb from pure ice with upper bounds for the surface binding energies of 0.16 ± 0.02 and 0.26 ± 0.03 eV, respectively. Above 150 K, N2O4 desorption follows first-order kinetics and is well described by the Arrhenius parameters Ea = 0.39 ± 0.04 eV and A = 10((15.4±1.2)) s(-1), while a stable N2O4 adlayer is formed at lower temperatures. A fraction of incoming N2O5 reacts to form HNO3 on the ice surface. The N2O5 desorption rates are substantially lower on pure water ice (Arrhenius parameters: Ea = 0.36 ± 0.02 eV; A = 10((15.3±0.7)) s(-1)) than on HNO3-covered ice (Ea = 0.24 ± 0.02 eV; A = 10((11.5±0.7)) s(-1)). The N2O5 desorption kinetics also sensitively depend on the sub-monolayer coverage of HNO3, with a minimum in N2O5 desorption rate at a low but finite coverage of HNO3. The studies show that none of the systems with resolvable desorption kinetics undergo ordinary desorption from ice, and instead desorption likely involves two or more surface states, with additional complexity added by coadsorbed molecules.

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Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films

Hammerich

Finlayson-Pitts

Gerber

2015

Phys. Chem. Chem. Phys.

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Nitryl chloride (ClNO2) and nitrosyl chloride (ClNO) are potential sources of highly reactive atmospheric chlorine atoms, hence of much interest, but their formation pathways are unknown. This work predicts production of these nitrogen oxychlorides from ab initio molecular dynamics (AIMD) simulations of N2O5 or an NO2 dimer on the surface of a thin film of water which is struck by gaseous HCl. Both of these heterogeneous reactions proceed at the liquid/vapor interface by an SN2 mechanism where the nucleophile is chloride ion formed from the ionization of HCl on the aqueous surface. The film of water enhances the otherwise very slow gas phase reaction to occur by (1) stabilizing and localizing the adsorbed N2O5 or NO2 dimer so it is physically accessible for reaction, (2) ionizing the impinging HCl, and (3) activating the adsorbed oxide for nucleophilic attack by chloride. Though both nitrogen oxychloride products are produced by SN2 reactions, the N2O5 mechanism is unusual in that the electrophilic N atom to be attacked oscillates between the two normally equivalent NO2 groups. Chloride ion is found to react with N2O5 less efficiently than with N2O4. The simulations provide an explanation for this. These substitution/elimination mechanisms are new for NOx/y chemistry on thin water films and cannot be derived from small cluster models.

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The reaction of N₂O₅ with H₃O⁺: A first‐principles direct molecular dynamics study of acid‐catalyzed reactive uptake of N₂O₅

Cited by 4 publications

References 24 publications

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Interactions of N₂O₅ and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films

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The reaction of N2O5 with H3O+: A first‐principles direct molecular dynamics study of acid‐catalyzed reactive uptake of N2O5

Cited by 4 publications

References 24 publications

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Ab initio and semi-empirical Molecular Dynamics simulations of chemical reactions in isolated molecules and in clusters

Interactions of N2O5 and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl−on aqueous films

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The reaction of N₂O₅ with H₃O⁺: A first‐principles direct molecular dynamics study of acid‐catalyzed reactive uptake of N₂O₅

Interactions of N₂O₅ and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics

Mechanism for formation of atmospheric Cl atom precursors in the reaction of dinitrogen oxides with HCl/Cl⁻on aqueous films