Corrected entry: After the incident with the runaway coach, Maverick is walking away and Annabelle trips or pretends to trip and falls against his leg. When she does she accidentally fires his holstered pistol. It would be impossible for her to do that as the pistol a single-action revolver, which means she would have to cock the hammer (pulling it up and away from the ground) and THEN pull the trigger, also up and away from the ground.
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Correction: No, it is not impossible. Annabelle could have half (or less) cocked the hammer and then let it slide back. Consequently, it could have hit a bullet and caused a shot. This accident happened very often in the "Old West", so often that most revolver-users just loaded five bullets into their revolvers and let the hammer rest on an unloaded chamber. Maverick apparently didn't, but that is not a mistake.