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Carlisle falls for Elena the first time they meet at 10 and never stops loving her (his love for her is what gets him through the war)
In chapter 11, Leo confesses that he has been in love with Christina for over 10 years, and they have known each other for 11 years; Leo is 18; he must have been 7 or 8 when he fell in love with Chris.
He seems to have been in love with her since childhood
In chapter 22, you learn that Vlad and Lily had an encounter once when they were kids (pre-teens); it seems that Vlad had fallen in love with her at that time, meaning it was probably love at first sight
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