So we see that the two excited dipoles corresponding to the S0 ® S1 and the S0 ® S2 transitions may be oriented at an arbitrary angle  - in the extreme case this angle could be 90o.  After the excitation process, however, regardless of whether the absorption process corresponded to the S0 ® S1 or the S0 ® S2 transition, rapid thermalization leaves the excited fluorophore in the S1  level.  The orientation of the excited dipoles will thus now possess a different average orientation than the absorption dipoles originally photoselected by the exciting light.
This situation is depicted below:
X
Y
A
E
S0 ® S2
S1 ® S0
ll
I
^
I
Z
Dipole V