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The second experimental question is that inhibition methods 170,165) and isotope methods 169,171~ give the relative quantum yield for I and II with conflicting results. At long wavelengths the latter method favors I, the former II. CI method and the "point system" in the selection of the configurations). Both sets of potential energy curves exhibit the same behavior. One is shown below (Fig. 10). 39 A. 30 ,,->. 40 =. ) Fig. 1 0 . ' P o t e n t i a l e n e r g y c u r v e s for t h e dissociation of f o r m a l d e h y d e into r a d i c a l p r o d u c t s .

If we use the general form (45) of the effective hamiltonian, the energy of the excited i--~l triplet state is given by: OCC 1 OCt + (x - ~) 2 (Kj, + Kj~) + (x - 1) K~ t (47) + { (x - l) ( J . + J u ) (The energy of the parent singlet is obtained by simply adding 2 Ka). The advantage of this method is its simplicity and low cost. For that reason, it is very often used to minimize excited-state structures or to scan large regions of excited-state potential energy surfaces. The major part of the photochemical problems examined in the second section of this article is treated within this framework.

39 A. 30 ,,->. 40 =. ) Fig. 1 0 . ' P o t e n t i a l e n e r g y c u r v e s for t h e dissociation of f o r m a l d e h y d e into r a d i c a l p r o d u c t s . } a n d { H C O . (2A ") + H . }. T h e first t w o t r i p l e t s - - t h e low-lying 3A 2 nrc* s t a t e a n d t h e h i g h - l y i n g 3A 1 rrrc* s t a t e - - a r e also r e p r e s e n t e d (/k)9o) In the dissociation process the ~*(2bl)MO of the n=* state changes into a pure 1 s orbital of hydrogen while acquiring some fairly large 3 s character in the intermediate region (C--H distance ~ 5 au).

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Triplet States I by Boschke F.L.


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