Temperature dependence of the photoequilibrium ratio. Adapted from Ref. 31.
Stimulated emission and bleach kinetics of [panel (A)] and [panel (B)] at 30 K (gray) and 15 K (black). The change of absorbance is given in units of optical density (OD). The inset of panel (A) represents the decay of the excited state absorption of .
Response of and after exciting . Panel (A) shows the bleach of after 200 ps and panel (B) that of at 200 ns. Gray and black lines compare the response at 30 and 15 K, respectively. The change of absorbance is given in units of OD.
Possible arrangement of the free energy surfaces of the various vibrational states as a function of a generalized solvation coordinate. The black circles mark the positions where nonadiabatic proton transfer between cis- and trans-HONO can take place in an essentially barrierless manner, explaining the increase in the rate as the temperature is decreased.
Fit results for vibrational relaxation of the OH-stretch vibration and the overall cooling into the matrix for both trans and cis HONOs.
Article metrics loading...
Full text loading...