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Investigation of the addition/elimination reaction pathways from the radical intermediate
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Image of FIG. 1.
FIG. 1.

Partial potential energy surface for calculated at the level of theory. All energies are in kcal/mol, corrected for the zero point energy, and relative to INT2, which is set as the zero of energy.

Image of FIG. 2.
FIG. 2.

TOF spectrum of at a source angle of 25°. The data, with constant background subtracted, were accumulated for 275 000 laser shots. The open circles correspond to the data points and the solid and dot-dashed lines represent the forward convolution fits to the spectrum from the given in Fig. 3.

Image of FIG. 3.
FIG. 3.

Total recoil KE distribution derived from forward convolution fitting the data shown in Fig. 2. The high recoil KE portion of the distribution shown in solid line corresponds to C–Cl fission events that produce radicals that subsequently access the product channel. In contrast, the lower recoil KE portion of the distribution shown in dot-dashed line does not.

Image of FIG. 4.
FIG. 4.

Chlorine spectrum taken at the University of Chicago using electron bombardment ionization and shots with constant background subtraction. The open circles are the data points, and the solid line is the fit calculated from the solid line portion of the in Fig. 3. The low recoil KE portion of the is not used because the pulsed nozzle created a nonconstant background at longer flight times, so the data are not high enough quality to discern that contribution.

Image of FIG. 5.
FIG. 5.

TOF spectrum for acrolein, , using photoionization, accumulated for 200 000 laser shots with constant background subtraction. The open circles represent the data points, and the solid line shows the poor fit to the data if one uses the entire C–Cl fission in Fig. 3 to predict the velocity of the acrolein products (the loss of a H atom from the momentum-matched radical to the Cl atom does not appreciably alter the acrolein product velocity). The dashed line fit, calculated from the dashed line in Fig. 6, reveals which subset of the momentum-matched radicals access the product channel.

Image of FIG. 6.
FIG. 6.

Comparison of the high KE portion of the (solid line) and the (dashed line). The distribution lacks the low recoil KE portion corresponding to the slow tail present in Fig. 2. The also deviates from the at the higher recoil translational energies, beginning at . The relative normalization of the two ’s is arbitrarily set to the statistical prediction for the product branching to the subsequent channel.

Image of FIG. 7.
FIG. 7.

TOF spectra for , 29, 28, and 27 at a source angle of 25° and an ionization energy of . Each set was accumulated for 200 000 shots and has the measured time-dependent background subtracted, except for spectrum that used 300 000 shots and constant background subtraction.

Image of FIG. 8.
FIG. 8.

The upper frame shows the raw image of obtained by photodissociating at and probing with via the transition. The lower frame shows the raw image of obtained by photodissociating at and probing with via the transition. The laser polarization is in the vertical direction as marked by the double-headed arrow, and each raw image is .

Image of FIG. 9.
FIG. 9.

Total center-of-mass translational energy distributions for the ground (dotted line) and excited (dashed line) states of chlorine, . The overall fit, after accounting for the proper line strength factor (Ref. 45) is given by the solid line.

Image of FIG. 10.
FIG. 10.

Comparison of the recoil translational energy distributions for using tunable VUV detection or velocity map imaging with REMPI ionization. The solid line corresponds to the distribution from the crossed laser-molecular beam apparatus having tunable VUV ionization, and the dashed line corresponds to the velocity map imaging distribution.

Image of FIG. 11.
FIG. 11.

Statistical rate constants predicted for the unimolecular dissociation of the INT 1 radical intermediate for the three dominant product channels observed in this work. The barriers used are those shown in Fig. 1, adjusted for the energy difference between INT1 and INT2.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Investigation of the O+allyl addition/elimination reaction pathways from the OCH2CHCH2 radical intermediate