The harpooning mechanism as evidenced in the oxidation reaction of the Al atom

Li, Fangfang; Dong, Chunsheng; Chen, Jun; Liu, Jiaxing; Wang, Fengyan; Xu, Xin

doi:10.1039/c7sc03314a

Cited by 18 publications

(23 citation statements)

References 48 publications

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“…The observation that the D 2 PES is associated with charge transfer is indicative of the harpoon mechanism. Traditionally, the harpoon mechanism has been invoked to treat the electron transfer between alkali metals and halogens (e.g., K and Br 2 ) − and more recently between NO ( A 2 Σ + ) and O 2 , NO, N 2 , and SO 2 . ,,,,,, The trend of harpoon-style electronic quenching between NO ( A 2 Σ + ) and nonhalogen collision partners has been shown to occur as a result of electron density transferring from the NO ( A 2 Σ + ) Rydberg electronic state, which is more facile to ionize, and onto electronegative atoms in the molecular collision partner. The first stage of the harpoon mechanism can be described as the transfer of the unpaired valence electron of NO to the molecular collision partner.…”

Section: Discussionmentioning

confidence: 99%

“…To further assess the extent to which the harpoon mechanism is relevant for ON + N 2 and ON + CO, we evaluated the distance at which the harpoon mechanism predicts that the electron transfer will occur: . − The adiabatic ionization energy (IE) of the D 2 ( A 2 Σ + ) state of NO was calculated to be 3.776 eV at the EOM-EA-CCSD/d-aug-cc-pVTZ//EOM-EA-CCSD/aug-cc-pVDZ level of theory. The electron affinities (EAs) of N 2 and CO were estimated to be −2.32 eV and −1.50 eV, respectively, based on the experimentally determined positions of the lowest-energy N 2 – and CO – resonances .…”

Section: Discussionmentioning

confidence: 99%

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Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

et al. 2021

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Intermolecular interactions, stereodynamics, and coupled potential energy surfaces (PESs) all play a significant role in determining the outcomes of molecular collisions. A detailed knowledge of such processes is often essential for a proper interpretation of spectroscopic observations. For example, nitric oxide (NO), an important radical in combustion and atmospheric chemistry, is commonly quantified using laser-induced fluorescence on the A 2 Σ + ← X 2 Π transition band. However, the electronic quenching of NO (A 2 Σ + ) with other molecular species provides alternative nonradiative pathways that compete with fluorescence. While the cross sections and rate constants of NO (A 2 Σ + ) electronic quenching have been experimentally measured for a number of important molecular collision partners, the underlying photochemical mechanisms responsible for the electronic quenching are not well understood. In this paper, we describe the development of high-quality PESs that provide new physical insights into the intermolecular interactions and conical intersections that facilitate the branching between the electronic quenching and scattering of NO (A 2 Σ + ) with H 2 , N 2 , and CO. The PESs are calculated at the EOM-EA-CCSD/d-aug-cc-pVTZ//EOM-EA-CCSD/aug-cc-pVDZ level of theory, an approach that ensures a balanced treatment of the valence and Rydberg electronic states and an accurate description of the open-shell character of NO. Our PESs show that H 2 is incapable of electronically quenching NO (A 2 Σ + ) at low collision energies; instead, the two molecules will likely undergo scattering. The PESs of NO (A 2 Σ + ) with N 2 and CO are highly anisotropic and demonstrate evidence of electron transfer from NO (A 2 Σ + ) into the lowest unoccupied molecular orbital of the collision partner, that is, the harpoon mechanism. In the case of ON + CO, the PES becomes strongly attractive at longer intermolecular distances and funnels population to a conical intersection between NO (A 2 Σ + ) + CO and NO (X 2 Π) + CO. In contrast, for ON + N 2 , the conical intersection is preceded by an ∼0.40 eV barrier. Overall, our work shines new light into the impact of coupled PESs on the nonadiabatic dynamics of open-shell systems.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

et al. 2021

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“…The time-sliced ion velocity imaging experiment was performed in our crossed-molecular beam setup . A single molecular beam was used in this photodissociation experiment .…”

Section: Experimental Methodsmentioning

confidence: 99%

“…The time-sliced ion velocity imaging experiment was performed in our crossed-molecular beam setup. 34 A single molecular beam was used in this photodissociation experiment. 35 Briefly, formic acid vapor was seeded in neon and expanded into the high vacuum via a heated Even-Lavie valve operating at 150 °C to reduce cluster formation.…”

Section: Experimental Methodsmentioning

confidence: 99%

Roaming Dynamics in the Photodissociation of Formic Acid at 230 nm

Jia-Xing

et al. 2019

J. Phys. Chem. A

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Roaming dynamics is observed in the photodissociation of formic acid (HCOOH) at 230 nm by using the slice imaging method. In combination with rotational state selective (2 + 1) resonance-enhanced multiphoton ionization of the CO fragments, the speed distributions of the CO fragments exhibit a low recoil velocity at low rotational levels of J = 9 and 20, while the velocity distributions of CO at high rotational levels of J = 30 and 48 show a relatively large recoil velocity. The experimental results indicate that the roaming of OH radical should be related with the formation of CO + H 2 O channel at the present photolysis energy. Unlike the roaming pathways occurring in H 2 CO that can be described by loose flat potential, our CO speed distribution analysis suggests the presence of a "tight" flat potential in the roaming dynamics of HCOOH molecules.

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“…The study of gas phase elementary reactions, in the absence of the solvent and under single collision events, more directly highlighted the role of CT. In this regard, we can mention: i) the harpooning processes, as evidenced in the oxidation reactions between a metal atom (mainly an alkaline metal) and a species with high electron affinity − ; ii) the Coulomb explosions of molecular dications , ; iii) the formation of excimer compounds which are involved in powerful UV lasers , ; iv) the chemi-ionization reactions (ChemI). − Many studies focused on individual aspects of these phenomena, but still today, there is not a unifying description of them.…”

Section: Introductionmentioning

confidence: 99%

Electronic Rearrangements and Angular Momentum Couplings in Quantum State-to-State Channels of Prototype Oxidation Processes

2021

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An innovative theoretical method to describe the microscopic dynamics of chemi-ionization reactions as prototype oxidation processes driven by selective electronic rearrangements has been recently published. It was developed and applied to reactions of Ne* atoms excited in their metastable 3 P J state, and here, its physical background is extensively described in order to provide a clear description of the microscopic phenomenon underlying the chemical reactivity of the oxidative processes under study. It overcomes theoretical models previously proposed and reproduces experimental results obtained in different laboratories. Two basic reaction mechanisms have been identified: (i) at low collision energies, a weakly bounded transition state is formed which spontaneously ionizes through a radiative physical mechanism (photoionization); (ii) in the hyperthermal regime, an elementary oxidation process occurs. In this paper, the selectivity of the electronic rearrangements triggering the two mechanisms has been related to the angular momentum couplings by Hund’s cases, casting further light on fundamental aspects of the reaction stereodynamics of general interest. The obtained results allow peculiar characteristics and differences of the terrestrial oxidizing chemistry compared to that of astrochemical environments to be highlighted.

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The harpooning mechanism as evidenced in the oxidation reaction of the Al atom

Abstract: The harpooning model is firstly evidenced by the maximum impact parameter derived from AlO(Nmax) products with speed v′ ≈ 0 from the Al + O2 reaction.

Cited by 18 publications

References 48 publications

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

Roaming Dynamics in the Photodissociation of Formic Acid at 230 nm

Electronic Rearrangements and Angular Momentum Couplings in Quantum State-to-State Channels of Prototype Oxidation Processes

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The harpooning mechanism as evidenced in the oxidation reaction of the Al atom

Abstract: The harpooning model is firstly evidenced by the maximum impact parameter derived from AlO(Nmax) products with speed v′ ≈ 0 from the Al + O2 reaction.

Cited by 18 publications

References 48 publications

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A2Σ+) with H2, N2, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A2Σ+) with H2, N2, and CO: Intermolecular Interactions Drive Collision Outcomes

Roaming Dynamics in the Photodissociation of Formic Acid at 230 nm

Electronic Rearrangements and Angular Momentum Couplings in Quantum State-to-State Channels of Prototype Oxidation Processes

Contact Info

Product

Resources

About

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes