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From Proto-Hellenic*ə-, from Proto-Indo-European*n̥-. The form ἀν-(an-) appears when followed by a laryngeal and a vowel: that is, in an open syllable of the n̥HV- form. Akin to νη-(nē-), νᾱ-(nā-) and νω-(nō-), which are closed-syllable reflexes of the n̥h₁C-, n̥h₂C-, n̥h₃C- forms, respectively.
The alpha privativum, used to make words that have a sense opposite to the word (or stem) to which the prefix is attached. It is also known as privative a and alpha privative; a-, ab-, an-, anti-, contra-, de-, dis-, ex-, il-, im-, in-, ob-, ne-, non-, not, un-
Usage notes
The alpha is usually short, but long when added to a stem that begins with three short syllables. Thus, words such as ἀ-δάματος(a-dámatos) begin with long alpha in Epic, and frequently also in Lyric, Tragic, or Comic poetry. ἀθάνατος(athánatos) and all its compounds always have long alpha.