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In photodissociation of trans-formic acid (HCOOH) at 193 nm, we have observed two molecular channels of CO + H2O and CO2 + H2 by using 1 μs-resolved Fourier-transform infrared emission spectroscopy. With the aid of spectral simulation, the CO spectra are rotationally resolved for each vibrational state (v = 1-8). Each of the resulting vibrational and rotational population distributions is characteristic of two Boltzmann profiles with different temperatures, originating from either transition state pathway or OH-roaming to form the same CO
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