Ultrafast control of the LnF+/LnO+ ratio from Ln(hfac)3.
Phys Chem Chem Phys
; 26(22): 15850-15855, 2024 Jun 06.
Article
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| MEDLINE
| ID: mdl-38682860
ABSTRACT
The photo-induced dissociative ionization of lanthanide complexes Ln(hfac)3 (Ln = Pr, Er, Yb) is studied using ultrafast shaped laser pulses in a time-of-flight (TOF) mass spectrometry setup. Various fluorine and Ln-containing mass fragments were observed, which can be interpreted by the photo-fragmentation mechanistic pathway involving C-C bond rotation processes proposed previously. A set of experiments used pulse shaping guided by closed-loop feedback control to identify pulses that optimize the ratio of LnF+/LnO+. In agreement with previous studies in which very little LnO+ was observed, broad pulses were found to maximize the LnF+/LnO+ ratio, which involves metal-ligand bond-breaking followed by bond rotation and bond rearrangement. In contrast, a transform limited (TL) pulse favored the formation of LnO+. Finally, the recently developed experimental control pulse slicing (CPS) technique was applied to elucidate the dynamics induced by fields that either maximize or minimize the LnF+/LnO+ ratio, which also indicates that longer laser pulses facilitate LnF+ formation during the C-C bond rotation dissociative-ionization process.
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MEDLINE
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Phys Chem Chem Phys
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BIOFISICA
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QUIMICA
Año:
2024
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Article