TOFMS of the photoionized MB containing (5%) and (5%) in Xe buffer gas at nozzle pressure of 2.5 atm: (a) only the photoionization (probe) pulse at 193 nm (3 mJ/pulse; laser focused onto spot, ), averaging over 128 laser pulses; (b) both excitation (; 5 mJ/pulse; focused onto 0.4 mm diameter spot, ), and probe pulses [the same parameters as in (a)] at zero delay between the two, averaging over 128 laser pulses; (c) only the photoionization (probe) pulse at 193 nm (3 mJ/pulse; laser focused onto spot, ), averaging over 512 laser pulses.
radical yield dependence on the excitation laser pulse energy: the -band and -band ; photoionization is induced by ArF excimer laser .
REMPI action spectrum of the line profile measured for two lines of : the -band and -band .
(1) REMPI action spectra of the vdW complexes. (a) Fitted spectrum. (b) Experimental spectrum measured for excitation radiation tuned within the spectral interval corresponding to the excitation of the molecule at the maximum of its absorption line in the -band; . (2) REMPI action spectra of the vdW complexes measured in the presence of both the excitation [-band; , ] and the tunable probe pulse.
Structures of the nonplanar vdW complex (a) and the (HOOSCCH) intermediate (b).
(a) REMPI action spectra of the radical recorded as in Fig. 4. (b) REMPI spectrum of the line recorded at resolution.
The IR emission spectra of the HOSO radical measured for excitation radiation at the maximum of the -band; absorption. The spectra shown were scanned at 1 and delay times, respectively.
Kinetic curves of the IR emission signals integrated over the respective IR emission bands [-band; (). (a) Kinetics in the entire measured time range. (b) Reduced time range, , for the integrated IR emission of the 910 and bands.
Signal dependence on the delay time between excitation radiation pulse [-band; , ] and REMPI probing radiation pulse . Circles correspond to HOSO and squares to , the fitted curve is shown by a solid line.
(a) Potential curve of the reaction (2). Configuration of the transition state. (b) 2D potential surface of the reaction (23).
Intensity and assignment of the TOFMS lines. The mixture at 2.5 atm nozzle pressure was used. Photoionization was performed at 193 nm, time range.
Rotational constants of the ground and excited electronic states of the vdW complex. The analyzed spectrum was scanned in the range of the -band [ rotational line]. The same values obtained from analysis of the MW spectra of the same complex for electronic ground state were taken from Ref. 33.
Values of the fundamental frequencies of the HOSO radical modes observed in the FTIR spectrum (Fig. 6) and the values of the diagonal anharmonicity factors for these modes.
Decay rates of the IR emission integrated over each of the spectral bands (Fig. 7).
The values obtained for different IR active modes of HOSO radical, extrapolated to zero time.
Geometrical parameters of the transition state of the vdW complex and of the intermediate. Calculations predict that acetylene is planar in the transition state and has cis-configuration, HOSO is also planar with structure, and CCH fragment is linear [coupled cluster/ and QCISD/ method].
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