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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 ( / = 70174.5(20) cm−1) was determined.


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