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On the adiabatic ionization energy of the propargyl radical
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19. C.-Y. Ng, private communication (2013), A simulation of the spectrum published in Ref. 7 carried out with the reversed spin-statistical factors leads to an ionization energy in good agreement with our new result.
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The photoionization and pulsed-field-ionization zero-kinetic-energy photoelectron spectra of the propargyl radical have been recorded in the vicinity of the origin of the photoionizing transition. An internally cold sample of propargyl with a rotational temperature of ∼45 K was produced in a supersonic expansion of 1,3-butadiene in helium. Propargyl was generated by excimer laser (ArF, 193 nm) photolysis of 1,3-butadiene in a quartz capillary mounted at the exit of a pulsed valve. The rotational structure of the origin band of the photoelectron spectrum was partially resolved and an improved value of the adiabatic ionization energy of propargyl (E I/hc = 70174.5(20) cm−1) was determined.
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