This is not about the theme, but the actual soundtrack.
My personal favs (in no order) are Sinatra - You Only Live Twice, Simon - Nobody Does it Better, Bassey - Diamonds Are Forever, Easton - For Your Eyes Only and Coolidge - All Time High. Surprisingly I kinda like that one Garbage did...ummm... World is Not Enough.
Adele and Skyfall is way up there. Better than the movie until I watch it. When is it out on BluRay?, LOL!