Photogeneration of free charge carriers in π-conjugated polymers with bulky side groups

► We model photogeneration of free charge carriers in poly{1-[4-(trimethylsilyl)phenyl]-2-phenylacetylene}. ► We can explain why the photogeneration dependences of free charge carriers on electric field doesn't saturate at low fields. ► We find a significant coupling between excited and charge transfer states at low field.