Typical mass spectra of -propyl nitrite, recorded at the zero in time, using pump and probe. Without pyrolysis (lower trace) only a negligible amount of ethyl is visible. When the pyrolysis is turned on (upper trace) intense signals at (ethyl) and 30 (NO, ) appear.
Time-dependent ion signal of ethyl, (open circles) and (NO, , open diamonds, shifted by units for ease of viewing). Positive delay times correspond to the pump pulse preceding the probe pulse. The signal was fitted by a Gaussian with a (dotted line) and provided an instrument response function (irf) as well as a zero in time. An accurate fit of the ethyl signal (full line) was only possible when the irf was convoluted with a monoexponential decay of .
The relevant electronic states of the propargyl radical. The transition excited by radiation is associated with a excitation. The energies of the states are only known from computations (Ref. 39).
Typical mass spectra of propargyl bromide, recorded at the zero in time, using pump and probe. Without pyrolysis (lower trace), the largest signal at , corresponds to toluene and a substantial amount of propargyl is present due to photolysis or dissociative photoionization of the precursor. The former is added as a stabilizer to commercial and can be resonantly excited at . When the pyrolysis is turned on (upper trace) the major part of the propargyl signal is due to pyrolyzed precursor. An additional signal at can be assigned to benzyl, originating from pyrolysis of toluene.
The time-dependent ion signal of propargyl (open circles) is fitted (solid line) by a convolution of a Gaussian with a monoexponential decay of . A small residual signal at large delay times is visible.
The time-dependent ion signal of benzyl (, open circles) is fitted (solid line) by a convolution of a Gaussian with a monoexponential decay of .
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