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Electronic state selectivity in dication-molecule single electron transfer reactions: NO(2+) + NO.

Michael A Parkes¹, Jessica F Lockyear, Detlef Schröder

¹Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ, United Kingdom.

Physical Chemistry Chemical Physics : PCCP

|August 16, 2011

Summary

Single-electron transfer between doubly charged and neutral nitric oxide (NO) ions was investigated. Unlike similar reactions, both product ions behaved identically, supporting new theories on electron transfer selectivity.

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Published on: December 29, 2016

Area of Science:

Chemical Physics
Physical Chemistry
Atomic and Molecular Collisions

Background:

Dication-molecule single-electron transfer (SET) reactions are crucial for understanding charge transfer processes.
Investigating electronic state selectivity in these reactions provides insights into fundamental chemical dynamics.
Previous studies on CO2(2+)/CO2 and O2(2+)/O2 systems showed complex reactivity patterns.

Purpose of the Study:

To study the single-electron transfer reaction between the nitric oxide dication (NO(2+)) and neutral nitric oxide (NO).
To test recent theoretical models concerning electronic state selectivity in dicationic SET reactions.
To compare the reactivity of the NO(2+)/NO system with analogous dication-molecule systems.

Main Methods:

Utilized a position-sensitive coincidence technique to analyze the products of the collision.
Focused on the electron transfer dynamics between NO(2+) and NO.
Examined the behavior of the resulting NO(+) ions.

Main Results:

The electron transfer reaction between NO(2+) and NO produced two NO(+) ions.
Crucially, both product NO(+) ions exhibited identical behavior, irrespective of their origin (from NO(2+) or NO).
This finding contrasts sharply with previously observed reactivity in CO(2)(2+)/CO(2) and O(2)(2+)/O(2) systems.

Conclusions:

The identical behavior of the product ions strongly supports recent theoretical rationalizations for state selectivity in dication-molecule SET reactions.
The results align with propensity rules based on one-electron transitions.
This study provides a clear benchmark for understanding electron transfer mechanisms in dication-neutral molecule interactions.