There's a distinction between the calibre application and that subset of it which is used within calibre to view books while the calibre application is open and active. I noticed that if you quit the calibre application while viewing a book in calibre's reader, the reader mini-app stays open until you quit it too. I don't know of a way to use the calibre reader otherwise without having the calibre app open first. If in the Mac OS Finder Get Info box you select calibre as the app to open all pdf's, then doubleclick a pdf file in the Finder, that will open calibre if it's not already open. But that won't automatically open that file in calibre's reader, as far as I know. I haven't tried that because it's more useful to me to view the original file (if outside calibre) in Acrobat.
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