It is Assur to smoke on Yom Tov, especially in America, where we no longer view it as Shaveh L’chol Nefesh. However, if you do think that smoking is Muttar on Yom Tov, then there is no reason whatsoever not to smoke during Bein HaShmashos. Same with lighting candles if you’re actually going to be using the light immediately.
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