The infrared-driven cis-trans isomerization of HONO. II: Vibrational relaxation and slow isomerization channel

In a recent paper R. Schanz et al., J. Chem. Phys. 122, 044509 (2005)], we investigated the IR-driven cis-trans isomerization of HONO in a Kr matrix with the help of femtosecond IR spectroscopy. We found that isomerization occurs on a 20 ps time scale, however, with a cis-->trans quantum yield of only 10% that is significantly below the value reported in the literature (close to 100%). At the same time, we concluded that vibrational energy has not completely dissipated out of the molecule at the maximum delay time we reached in this study (500 ps). In order to verify whether additional, slower reaction channels exist, we extend the study here to delay times up to 100 ns. At a temperature of 32 K, we indeed find an additional isomerization channel on a 2 ns timescale, which increases the total cis-->trans quantum yield to approximately 30%. The trans-->cis quantum yield is approximately 7%. There is still a discrepancy between the quantum yields we observe and the literature values, however, we provide experimental evidence that this discrepancy is due to the different temperatures of our study. Vibrational cooling occurs on a 20 ns time scale, and cascades in a highly nonstatistical manner through one single normal mode (most likely the ONO bending mode nu(5)). Intermolecular energy dissipation into the rare gas matrix is more efficient than intramolecular vibrational energy redistribution and the matrix environment can certainly not be considered a weak perturbation.