Why do you want to catch her? I believe that attempting to catch her "red-handed" as it were would just send the wrong signal. It's fairly confrontational, when the best method to help somebody quit smoking is to be supportive.
With that in mind, I think it would be best to just have a talk with her, as opposed to trying to come up with evidence and catch her. Tell her you are concerned that she might be smoking, and whether she is or not doesn't matter to you, you just want to be there for her if she needs help quitting. She may not be upfront about it right away, but when she's ready she will come to you for help and when she does she's going to have a much better chance of quitting with the support and love of her family. That's going to create a much more hospitable and comfortable environment for the healing to begin. I can tell you, as a smoker, the last thing you want is confrontation because it has a tendency to make you want to smoke even more.
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