Abstract
The trans to cis photoisomerization of 4,4‘-dinitro-2,2‘-disulfonylstilbene (DS) was studied by laser-induced optoacoustic spectroscopy (LIOAS) in aereated neat water and in aereated aqueous solutions of various monovalent cations (NH4+, N(CH3)4+, Na+, K+, and Cs+) and the respective cis to trans photoisomerization only in the presence of NH4+. In every case, two single-exponential components were required to fit the data, one with an unresolved lifetime (<20 ns) for the appearance of the triplet state mixture T (the perpendicular triplet state 3p* in equilibrium with the lowest trans triplet state 3t*) and one with a longer lifetime of (75 ± 20) ns at 5.5 °C for the decay of the T mixture. The temperature dependence of the LIOAS amplitudes in combination with the determined isomerization quantum yields afforded a contraction of −(1.4 ± 0.15) ml/mol for the trans to T transition, whereas a smaller contraction of −(0.15 ± 0.15) ml/mol was obtained for the cis to T transition. The different values of the co...
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