Can you please install the "evtest" package and check with "sudo evtest"
that you actually get brightness keycodes every time you press these
keys? I suppose that is true as you write "Changing the shortcut to
execute "xfce4-terminal" seems to make the hotkey 100% consistent", so
the evdev events seem to be alright.
So this is most likely a bug in the XFCE service which reacts to these
key codes (I don't know exactly what that is), or possibly (but unlikely
according to your description) in the kernel if it does not synthesize
key codes correctly.
** Changed in: systemd (Ubuntu)
Status: Confirmed => Incomplete
** Package changed: systemd (Ubuntu) => xfce4-settings (Ubuntu)
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https://bugs.launchpad.net/bugs/1313220
Title:
Application Shortcuts (Hotkeys) Only Sometimes Work
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