a ere co Univ J foal 6 22 Unimolecular Processes Poy 12, Yi'y a ee pas (luminescence) transitions in which the molecule ofaphoton, Kaien toa lower electronic state by the emission : on. A radiative transition between states of the same multiplicity F described as fuorescence, A radiative transition between states o! Cifferent multiplicity is described as phosphorescence. © Radiationless transitions between isoenergetic vibrational levels of cit- fi ferent lectronic states. Such transitions are normally preceded vy Tadiationless thermal activation of the initial electronic stato, and/or followed by radiationless thermal de-activation of the final electronic State (Chapter 5), A radiationless transition between states of the same multiplicity Ls de: as internal conversion. One between states of different multiplicity is described as éntersystem crossing. Absorption transitions * @ 8-3, and S,--S, absorption is spin-allowed, and it corresponds to the main electronic absorption spectrum (Chapter 3). le 2 @) So -T; und Sy —T, absorption is spin-forbidden, but it can be obseived by using long light paths, intense light sources, or perturbation methods ($6.8). a 3. (iii) T, —_T, absorption is commonly observed by flash photolysis ($6.9). - A» 1, is populated by intersystem crossing [see (xiv) below] from S,, wh: \~ > is initially excited by an intense light flash, The transient absorption is : : observed during the T; excitation lifeti a u (iy) S;—S, absorption is observed by nanosecond flash photolysis ($3.10). §, is initially populated by an intense light fi short duration, and the transient absorption is observe ation lifeti Luminescence transitions . (¥) S; ~ Sp fiuorescence of short normal fluorescence emission (Ch 1 (vi) T, — Sy phosphorescence gen (~1 ~ 10* ms) than the fluo: ¢ transition (Chapter 6). (vii) 5, — Sp fluorescence has been ¢ azulene (§5.13), (viii) T, — Sp phosphore other compounds (§5. 2 @ T-Tf