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Intramolecular vibrational energy relaxation in nitrous acid (HONO)
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10.1063/1.2996355
/content/aip/journal/jcp/129/16/10.1063/1.2996355
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/16/10.1063/1.2996355

Figures

Image of FIG. 1.
FIG. 1.

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).

Image of FIG. 2.
FIG. 2.

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.

Image of FIG. 3.
FIG. 3.

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).

Image of FIG. 4.
FIG. 4.

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.

Tables

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Table I.

Vibrational frequencies (in ) of HONO in solid Kr.

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Table II.

Vibrational lifetimes.

Generic image for table
Table III.

Calculated and experimental anharmonic coupling constants of HONO (in ).

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/content/aip/journal/jcp/129/16/10.1063/1.2996355
2008-10-24
2014-04-17
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Intramolecular vibrational energy relaxation in nitrous acid (HONO)
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/16/10.1063/1.2996355
10.1063/1.2996355
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