Theoretical study of the F(2P) + NH3→ HF + NH2reaction on an accurate potential energy surface: dynamics and kinetics

Tian, Li; Zhu, Yongfa; Song, Hongwei; Yang, Minghui

doi:10.1039/c9cp02113b

Cited by 31 publications

(54 citation statements)

References 42 publications

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“…As discussed in a previous publication, 25 the neutral PES is constructed by fitting ~41000 ab initio energy points calculated at the unrestricted coupled cluster level with singles, doubles, and perturbative triples 52 with Dunning's augmented correlation-consistent polarized valence triple zeta basis set 53 and core electrons frozen (FC-UCCSD(T)-F12a/aug-cc-pVTZ) using the fundamental-invariant neural network (FI-NN) method. 54 An anion PES is newly constructed for this work by fitting a total of ~11000 energy points at the same level of theory used to construct the neutral PES.…”

Section: Theoretical Methodsmentioning

confidence: 99%

“…1) has recently been determined by fitting a large number of high-level ab initio points in full dimensionality. 25 Previous experimental work on the title reaction has studied the vibrational distribution of the HF product via infrared chemiluminescence [26][27][28] More recent crossed beam experiments by Yang and co-workers 29 have shown that the HF products (or DF in the F + ND3 reaction) are largely forward scattered with respect to the incoming F atom. Quasi-classical trajectory studies on the dynamics and kinetics of this reaction have been reported on an analytical PES, [30][31] and the calculated differential cross sections agreed reasonably well with the values determined by Yang.…”

Section: Introductionmentioning

confidence: 99%

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Transition State Spectroscopy of the F + NH3 Reaction

Babin

DeWitt

Lau

et al. 2022

Preprint

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Transition state spectroscopy experiments based on negative ion photodetachment directly probe the vibrational structure and metastable resonances that are characteristic of the neutral reactive potential energy surface (PES). Here, we study the five-atom reaction F + NH3 → HF + NH2 using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled FNH3¯ anions. Reduced-dimensional quantum dynamical simulations performed on a global potential energy surface show excellent agreement with the experimental results, allowing for the assignment of spectral structure and demonstrating that key dynamics of this bimolecular reaction are well described by this theoretical framework. Our combined experimental-theoretical study reveals features associated with a manifold of vibrational Feshbach resonances in the product well of the F + NH3 PES. At higher energies, the spectra reveal structure attributed to resonances localized across the transition state and into the reactant complex well, which may impact the bimolecular reaction dynamics.

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Section: Theoretical Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Transition State Spectroscopy of the F + NH3 Reaction

Babin

DeWitt

Lau

et al. 2022

Preprint

Self Cite

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“…Experimentally, while Walther and Wigner in 1983 [38] reported that the rate constants were practically independent of temperature in the range 250-369 K (where large uncertainties are present), Persky [39] reported inverse temperature dependence in the range 276-327 K in 2007. Theoretically, this reaction has also been studied [40][41][42][43][44][45][46][47]. In 1997, our lab developed the first analytical potential energy surface for this reactive system, PES-1997, which was semiempirical, i.e., it was fitted to theoretical and experimental information [42].…”

Section: The F( 2 P) + Nh3 Reaction: Does a Huge Number Of Points Gua...mentioning

confidence: 99%

Current Status of the X + C2H6 [X ≡ H, F(2P), Cl(2P), O(3P), OH] Hydrogen Abstraction Reactions: A Theoretical Review

2022

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This paper is a detailed review of the chemistry of medium-size reactive systems using the following hydrogen abstraction reactions with ethane, X + C2H6 ® HX + C2H5; X ≡ H, F(2P), Cl(2P), O(3P) and OH, and focusing attention mainly on the theoretical developments. These bimolecular reactions range from exothermic to endothermic systems and from barrierless to high classical barriers of activation. Thus, the topography of the reactive systems changes from reaction to reaction with the presence or not of stabilized intermediate complexes in the entrance and exit channels. The review begins with some reflections on the inherent problems in the theory/experiment comparison. When one compares kinetics or dynamics theoretical results with experimental measures, one is testing both the potential energy surface describing the nuclei motion and the kinetics or dynamics method used. Discrepancies in the comparison may be due to inaccuracies of the surface, limitations of the kinetics or dynamics methods, and experimental uncertainties that also cannot be ruled out. The paper continues with a detailed review of some bimolecular reactions with ethane, beginning with the reactions with hydrogen atoms. The reactions with halogens present a challenge owing to the presence of stabilized intermediate complexes in the entrance and exit channels and the influence of the spin-orbit states on reactivity. Reactions with O(3P) atoms lead to three surfaces, which is an additional difficulty in the theoretical study. Finally, the reactions with the hydroxyl radical correspond to a reactive system with ten atoms and twenty-four degrees of freedom. Throughout this review, different strategies in the development of analytical potential energy surfaces describing these bimolecular reactions have been critically analyzed, showing their advantages and limitations. These surfaces are fitted to a large number of ab initio calculations, and we found that a huge number of calculations leads to accurate surfaces, but this information does not guarantee that the kinetics and dynamics results match the experimental measurements.

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“…This assumption remains speculative even if the work from Ogawa [15] indirectly suggests that NH4F could be produced from the reaction of NH3 gas with some fragment of NF3 (formed by heating NF3). As a matter of fact, the formation of HF in the plasma can be expected to play a significant role in the overall chemistry and we can expect HF to be formed by the chain reactions (2-4) (well known in HF laser physics) [25,26,27,28,29,30]:…”

Section: Several Innovative Etching Processes Have Been Developed Recmentioning

confidence: 99%

Vacuum ultraviolet-absorption spectroscopy and delocalized plasma-induced emission used for the species detection in a down-stream soft-etch plasma reactor

Soriano

Cunge

Sadeghi

2020

Journal of Vacuum Science &Amp; Technology A: Vacuum, Surfaces, and Films

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The VUV-absorption spectroscopy (AS) and the emission spectroscopy (ES) from delocalized probe plasma, are implemented in the downstream chamber of a soft-etch industrial plasma reactor. A CCP plasma, running in the upper compartment in He/NF3/NH3/H2 mixtures at about one Torr, produces reactive species which flow through a shower head into a downstream chamber, where they can etch different µ-electronics materials: Si, SiO2, SiN,... The ES reveals the presence of F and H atoms, while the dissociation rates of NF3 and NH3 are deduced from the AS, as well as the density of HF molecules, produced by chemical chain-reactions between dissociation products of NF3, NH3 and H2.

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Theoretical study of the F(²P) + NH₃→ HF + NH₂reaction on an accurate potential energy surface: dynamics and kinetics

Abstract: Competition of the direct and indirect mechanisms in the hydrogen abstraction reaction between F and NH3.

Cited by 31 publications

References 42 publications

Transition State Spectroscopy of the F + NH3 Reaction

Transition State Spectroscopy of the F + NH3 Reaction

Current Status of the X + C2H6 [X ≡ H, F(2P), Cl(2P), O(3P), OH] Hydrogen Abstraction Reactions: A Theoretical Review

Vacuum ultraviolet-absorption spectroscopy and delocalized plasma-induced emission used for the species detection in a down-stream soft-etch plasma reactor

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