There are many reasons this could happen.
- It's possible to activate siri on an Apple Watch without pressing any buttons or even saying "hey siri." There is a setting called "Raise to Speak" - if that is on, a simple turn of the wrist and saying any words that sound even close to "one alarm" could inadvertently set a 1:00pm alarm on the watch. It's very likely this is what happened, and there is no reason to be worried. If you don't like this setting, it can be disabled in settings on the Apple Watch.
- The Apple Watch mirrors any alarms or timers set on the phone, too.
- If your wife has the timer complication on her watch face, it would be very easy to tap it accidentally and inadvertently start a timer.
Again, none of these should be cause for concern. It has happened to all of us at some point!