^{1}, Sarah M. Harper

^{1}, Sunny W.-P. Hu

^{1}and Stephen D. Price

^{1,a)}

### Abstract

We have studied the potentially ionospherically significant reaction between with using position-sensitive coincidence spectroscopy. We observe both nondissociative and dissociativeelectron transferreactions as well as two channels involving the formation of . The product is formed together with either and O in one bond-forming channel or and N in the other bond-forming channel. Using the scattering diagrams derived from the coincidence data, it seems clear that both bond-forming reactions proceed via a collision complex . This collision complex then decays by loss of a neutral atom to form a daughter dication ( or ), which then decays by charge separation to yield the observed products.

The authors acknowledge the financial support of the EPSRC, the EU (RTN1-2000-00025), and the Leverhulme Trust. One of the authors (C.R.) also acknowledges the support of the EPSRC via a DTA studentship. The authors are also grateful for helpful discussions on theoretical methodology with Nik Kaltsoyannis and Natalie Lambert. The authors also gratefully acknowledge Roland Thissen and Odile Dutuit both for making their results on the reactivity of available prior to publication and for valuable discussions.

I. INTRODUCTION

II. EXPERIMENTAL ARRANGEMENT AND DATA PROCESSING

III. RESULTS AND DISCUSSION

A. Relative intensities of the different reactive channels

B. Formation of

1. Reaction energetics

2. Angular scattering

3. Minima on the potential-energy surface

C. Formation of

IV. CONCLUSION

### Key Topics

- Electron transfer
- 30.0
- Transfer reactions
- 29.0
- Collision induced chemical reactions
- 28.0
- Dissociation
- 18.0
- Time of flight mass spectrometry
- 15.0

## Figures

Schematic diagram of the experimental apparatus.

Schematic diagram of the experimental apparatus.

Section of the coincidence spectrum recorded following collisions of with at 7.1 eV. The spectrum clearly shows the two dissociative electron transfer reactions and the two bond-forming reactions that occur in this collision system [Eqs. (23)–(26)]. The horizontal line in the spectrum at the time of flight of is due to the contribution of false coincidences involving unreacted ions. See text for details.

Section of the coincidence spectrum recorded following collisions of with at 7.1 eV. The spectrum clearly shows the two dissociative electron transfer reactions and the two bond-forming reactions that occur in this collision system [Eqs. (23)–(26)]. The horizontal line in the spectrum at the time of flight of is due to the contribution of false coincidences involving unreacted ions. See text for details.

Plot of the intensity of reaction (25) in the coincidence pair spectrum against the intensity of reaction (23) as a function of the center-of-mass collision energy.

Plot of the intensity of reaction (25) in the coincidence pair spectrum against the intensity of reaction (23) as a function of the center-of-mass collision energy.

Scattering diagrams for (a) and and (b) and N formed in reaction (25), recorded following collisions of with at 7.1 eV, with respect to the velocity of the center of mass. The spectrum was recorded under conditions which collect the full angular scattering. The arrow labeled , which is drawn from the origin of the diagram marked by a dot, represents the direction of the velocity of the center of mass. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. Since , the data for is plotted in the upper semicircle of (a) and the data for in the lower semicircle. Similarly, the data for is plotted in the upper semicircle of (b) and the data for N in the lower semicircle. See text for details.

Scattering diagrams for (a) and and (b) and N formed in reaction (25), recorded following collisions of with at 7.1 eV, with respect to the velocity of the center of mass. The spectrum was recorded under conditions which collect the full angular scattering. The arrow labeled , which is drawn from the origin of the diagram marked by a dot, represents the direction of the velocity of the center of mass. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. Since , the data for is plotted in the upper semicircle of (a) and the data for in the lower semicircle. Similarly, the data for is plotted in the upper semicircle of (b) and the data for N in the lower semicircle. See text for details.

Internal frame scattering diagram showing the motion of and N formed in reaction (25), recorded following collisions of with at 7.1 eV, relative to that of . In this diagram is the radial coordinate and the angle between and is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for N in the lower semicircle. See caption for Fig. 4 and text for details.

Internal frame scattering diagram showing the motion of and N formed in reaction (25), recorded following collisions of with at 7.1 eV, relative to that of . In this diagram is the radial coordinate and the angle between and is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for N in the lower semicircle. See caption for Fig. 4 and text for details.

Internal frame scattering diagram showing the motion of and formed in reaction (25), recorded following collisions of with at 7.1 eV, relative to that of N. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for in the lower semicircle. See text for details.

Internal frame scattering diagram showing the motion of and formed in reaction (25), recorded following collisions of with at 7.1 eV, relative to that of N. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for in the lower semicircle. See text for details.

Internal frame scattering diagram showing the motion of and formed in reaction (26), recorded following collisions of with at 7.1 eV, relative to that of O. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for in the lower semicircle. See text for details.

Internal frame scattering diagram showing the motion of and formed in reaction (26), recorded following collisions of with at 7.1 eV, relative to that of O. In this diagram is the radial coordinate and , the angle between and , is the angular coordinate. The data for is plotted in the upper semicircle of the figure and the data for in the lower semicircle. See text for details.

## Tables

Geometric parameters of the “tetrahedral” singlet minima of determined by a optimization.

Geometric parameters of the “tetrahedral” singlet minima of determined by a optimization.

Geometric parameters of the “linear” triplet minima of determined by a optimization, with connectivity .

Geometric parameters of the “linear” triplet minima of determined by a optimization, with connectivity .

Relative energetics of the relevant reactant, product, and intermediate configurations for reaction (26).

Relative energetics of the relevant reactant, product, and intermediate configurations for reaction (26).

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