The thing to remember with caffeine is its half-life in non-smokers is 8 hours (it is 3 hours in smokers). I have a rule to never have any drink with caffeine after midday - if I break this rule even by an hour I suffer that night and the next day. Caffine is a morning drug.
The effects are 6 hours for me, less than 1 hour for my father (who smokes), and can last over 18 hours for my wife and mother-in-law.
I haven't seen the studies on caffiene half-life, but I suspect the variation is very high.
I personally take it early morning and after a siesta.