Chemistry in the laboratory by C W J Scaife; O T Beachley

By C W J Scaife; O T Beachley

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24 EDWARD K. C. LEE AND GARY L. LOPER the above data correspond to thermally equilibrated triplet S 0 2 molecules. 4 msec. These data were taken over a pressure range of 1-500 mtorr at 25°C using a cell with a spherical diameter of 35 cm (Briggs et al, 1975). This cell was much larger than the one used previously by Otsuka and Calvert (1971). ^) at 3631 Ä over a pressure range between 1 mtorr and approximately 20 torr. These data were obtained at 26°C using a 22 liter cell. 29 based upon their earlier data.

They suggested that a substantially larger Franck-Condon factor exists for ISC than for the Sj -JWL* S0 internal conversion (IC), H2co(S1) klc > H2co(Sj), (37) 3 due to a more bent geometry for Ύ1 than S^ An approximately 10 times smaller electronic coupling matrix element was expected for ISC than for IC, but it was thought to be nearly compensated for by the favorable Franck-Condon factor above, implicating v£ as an efficient accepting mode [see Eqs. (14) and (15)]. Therefore, they regarded the comparable values of /cisc^Tp1 and fcic < TF * for H2CO to be quite reasonable theoretically.

1977) suggested that the lowfluorescencequantum yield of the perturbed 234* level is simply associated with the greater nonradiative character of the pure 2*3242 or 2*4262 level which may decay by Sx -w-> S0 more rapidly than the pure 2341 level. More study is needed to obtain a detailed understanding of this interesting observation about the intramolecular, collisionless vibrational energy redistribution by time evolution of an optically prepared vibrational state. 8 nsec showed that despite the presence of an extensive S-T perturbation no changes in the fluorescence quantum yields of a number of perturbed levels were observed.

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