Congratulations to your wife on her new job -- I'm assuming this is a positive change.
Some questions ... how long does your wife have to wait before deciding and are the deductible year and the calendar year the same (or if not, when does the new year start)? If your wife can wait a few months (to sign up) and there's hope of planning ahead (stocking up on meds and so forth, or biting the cost) and hoping for the best (no ER visits in the final quarter), that could be one strategy. Also, when is her new employer's open enrollment? Again, it might make sense to stick with what you've got for this year and then switch over at the next opportunity.
I'm no expert on HSAs, but those are the thoughts/ideas that spring to mind.