Transient difference spectra of following the excitation of (gray lines), [panel (a), black lines] and [panel (b), black lines]. Vertical dashed lines labeled 4–1 mark the spectral positions of the four hot bands observed in the trans cooling. To facilitate comparison, the delay times are chosen such that population peaks in a certain hot band. The bands labeled with correspond to the direct anharmonic coupling between the pumped and probed vibrations (see text).
Three-dimensional representation of the transient difference spectra in the spectral range of HON bend (left column), stretch (middle column), OH stretch (right column), after exciting either (top row, the very top shows a stationary difference spectrum measured in a FTIR spectrometer as a reference), and/or (middle row), and (bottom row). Red color depicts negative stimulated emission and/or bleach signals, colors in green-cyan-blue-pink positive bands from either transient hot bands and/or the photoproduct. The positive bands are coded with a three digit label that represent pumped mode (first digit), probed mode (second digit), and the mode to which the probed mode anharmonically couples (third digit). Bands for which the assignment is speculative are labeled with an additional question mark.
Time traces extracted from Fig. 2 for the cis- bleach and stimulated emission (squares), the decay of cis-OH measured through band (circles) and the dynamics of the two bands and (rhombi and stars).
Cooling cascade after pumping , , and . Energy levels are drawn to scale; the energies of the overtones of the cooling mode (ONO bending) are taken from Ref. 7.
Vibrational frequencies (in ) of HONO in solid Kr.
Calculated and experimental anharmonic coupling constants of HONO (in ).
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