We present a theoretical and experimental study of the electronic structure of $N$-methyltrifluoroacetamide (FNMA) and examine the resonant Auger (RA) decay upon site- and state-specific excitation at the C $1s$, N $1s$, and O $1s$ edges. Based on the calculated energies for cationic states of $1h$ and $2h\text{−}1p$ configurations, we assign the peaks of recorded VUV photoelectron and RA spectra. Specifically, we identify the spectral features associated with participator and spectator RA decay. To aid in a deeper understanding of previous observations of limited site-specific bond breaking in FNMA, the influence of the site-specific excitation and the character of the Auger decay on the fragmentation is investigated using Auger electron ion coincidence experiments. Moreover, to investigate the potentially different capacity for selective bond cleavage of participator and spectator Auger states, we apply this technique to the spectator Auger state with the main electronic configuration of ${\left(31a^{\prime }\right)}^{-1}{\left(32a^{″}\right)}^{-1}{\left(34a^{″}\right)}^1$, which is well resolved in the experimental spectrum. Finally, the influence of the molecular excess energy and the electronic character of the RA final states on fragmentation is addressed. Based on our findings, we argue that the excess energy the FNMA molecule gains upon RA decay is the dominant factor determining the fragmentation pattern.

• Received 24 April 2020
• Accepted 27 August 2020

DOI:https://doi.org/10.1103/PhysRevA.102.032817

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Published by the American Physical Society