Ionization and electron excitation of fullerene molecules in a carbon nanotube. A variable temperature/voltage transmission electron microscopic study

TL;DR

This study uses variable-temperature and voltage transmission electron microscopy to identify five reaction pathways of fullerene molecules within carbon nanotubes, revealing how ionization and electron excitation contribute to radiation damage.

Contribution

It provides the first detailed mechanistic analysis distinguishing ionization and electron excitation pathways in radiation damage of fullerenes at atomic resolution.

Findings

Five reaction pathways identified for fullerene dimerization

Radical cation reactions dominate below 200 K

Excited-state reactions dominate above 350 K

Abstract

There is increasing attention to chemical applications of transmission electron microscopy, which is often plagued by radiation damage. The damage in organic matter predominantly occurs via ionization (radiolysis). Although radiolysis is highly important, previous studies on radiolysis have largely been descriptive and qualitative, lacking in such fundamental information as the product structure, the influence of the energy of the electrons, and the reaction kinetics. We need a chemically well-defined system to obtain such data, and have chosen as a model a variable-temperature and variable-voltage (VT/VV) study of the dimerization of a van der Waals dimer [60]fullerene (C60) to C120 in a carbon nanotube (CNT) as studied for individual reaction events at atomic resolution. We report here the identification of five reaction pathways that serve as mechanistic models of radiolysis damage. Two of them occur via a radical cation of the specimen generated by specimen ionization, and three involve singlet or triplet excited states of the specimen, as initiated by electron excitation of the CNT followed by energy transfer to the specimen. The pathways were distinguished by the pre-exponential factor and the Arrhenius activation energy. The prototypal reaction path is the radical cation reaction that we saw at <200 K, but, at >350 K, the excited-state reactions dominate. The results illustrate the importance of VT/VV kinetic analysis in the studies of radiation damage, and show that chemical ionization and electron excitation are inseparable but different mechanisms of radiation damage, which has so far been classified loosely under the single term "ionization."