(verb) enthral, fascinate, enchant
The word arrived in English from Latin in the 16th century in the literal sense of "make captive" or "capture", and was immediately extended to include the notion of "take over the mind", source of the modern meaning.
Shakespeare, however, uses the word only in its literal sense, as is usually made clear by the context. So, when Armado tells Costard, "Thou wert immured, restrained, captivated, bound" (Love's Labour's Lost, III.i.123) the older sense is reinforced by the accompanying synonyms.
Likewise, the military context leaves little room for doubt when the Countess talks about General Talbot sending "our sons and husbands captivate" (Henry VI Part 1, II.iii.41). But there is more chance of ambiguity when, in the same play (V.iii.107), Margaret reflects, on listening to Suffolk's wooing, that "women have been captivate ere now".
And the modern meaning is lurking in the wings when Adonis's horse is imagined to be leaping in order "to captivate the eye" (Venus and Adonis, 281) or York condemns the Queen for triumphing "Upon their woes whom Fortune captivates" (Henry VI Part 3, I.iv.115).