The reference I specifically remember (although I have read others) is in "Dark Sun" by Richard Rhodes. LeMay ordered overflights over the USSR and commented:
"Well, maybe if we do this overflight right, we can get World War III started."
I don't have my copy of Dark Sun handy, but there is a reference to the incident in this review:
http://www.geoffwisner.com/index.php/book_reviews/article/?t...
LeMay's belief in a "preventative" war was oddly rational - he believed that a conflict between the US and the USSR was inevitable and that therefore that US should strike before the USSR posed a strategic threat to the US (which it didn't really do until the mid 60s at the earliest).
Rhodes writes about the Cuban Missile Crisis:
"If John Kennedy had followed LeMay's advice, history would have forgotten the Nazis and their terrible Holocaust. Ours would have been the historic omnicide".