Cinnamoyloxy group state functions

The lowest triplet state energy calculated by the PPP method is 18755 cm"1 in accordance with the observed value. The MIM calculations show that the main contribution to Ti is the LE of cinnamoyloxy group (69 ) and the energy difference between Ti and T2 is only 3200 cm . We can understand from the small difference that the only one vibrational structure appears in Pig.5(b) and can also estimate that the vibrational structiure arises from the central double bond of cinnamoyloxy group and not from azide. The T2 state has the same character as the Ti state of phenylazide where the contribution of the LE function of azide group is remarkable(55.02 in this case). 

Table 3. The Contributions of Various Electronic Configurations of the HIM model for the State Functions of the PPP model of trans-Cinnamoyloxy Group %)...

Table 6. The Resemblance of the Sj State Function of Stilbene and the S2 State Function of Cinnamoyloxy Group-...

Table 2. The State Functions and MO of trans-Cinnamoyloxy Group...

Analyses of the Electronic Transitions of Poly(vinyl cinnamate). The concerted cycloaddition of cinnamoyloxy group is essentially the reaction of the central double bond. Therefore, we can expect to obtain the clearer image than that hitherto considered in the photochemical reaction if the contributions of the central double bond for the excited states are calculated quantitatively. It is known that the state functions of PPP model can be rewritten to the linear combinations of LE and CT(charge transfer) functions of MIM method(7 ) when we use the same atomic orbitals as the base functions (q ). Using the technique, the state functions in Table 2 are rewritten and the results are collected in Table 3 The relationship between these two methods is illustrated in Fig.1 (b), (c). 

---