TY - JOUR
T1 - Ultrafast control of the LnF+/LnO+ ratio from Ln(hfac)3
AU - Chen, Jiangchao
AU - Xing, Xi
AU - Rey-De-Castro, Roberto
AU - Rabitz, Herschel
N1 - Publisher Copyright:
© 2024 The Royal Society of Chemistry.
PY - 2024/4/19
Y1 - 2024/4/19
N2 - 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.
AB - 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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U2 - 10.1039/d4cp00337c
DO - 10.1039/d4cp00337c
M3 - Article
C2 - 38682860
AN - SCOPUS:85191829456
SN - 1463-9076
VL - 26
SP - 15850
EP - 15855
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 22
ER -