1- I don't know if it so much applies to LEDs as it applies to the interjunction capacitance of a diode, so, yes, by definition, it does apply to LEDs.
2- If you change the charging voltage to the LED, I would think all you'd really change is the point at which the voltage dropping from the LED would trip the PICs pin input from logic high to logic low...(one setup charges to 5v, take awhile to drop to logic 0, other setup only charges to 3v, doesn't take near as long to drop to logic 0).
Why do you want to 'speed up' the discharge process?
What end result AREN'T you getting now that you really want?
Just trying to get a handle on what you're after...
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