@ray53,
You can contact nearly anyone on Facebook, through Facebook, long as you aren't being actively blocked. However, if you are not friends, your private messages will be binned into what's called the "Other" folder. Most people don't check theirs too often. It's mainly considered to be the equivalent of a spam folder.
As for your wife's motivations, you know her far better than any of us ever would. Her explanation? I dunno if it's plausible. BTW, I'm married for 22+ years and have searched for exes, and am even FB friends with a few. For me, it was just to see what had happened to people I had known, and cared about. Whether the same is true for your wife is unknown.
PS Don't snoop in her account anymore.