Yes, you can use the HSA to pay for care for yourself, your spouse, and your dependents. However, the situation is a bit odd when it comes to children who you don't claim as tax dependents. The rules for medical insurance allow you to cover a child who is your dependent, or who would have been your dependent except that you file separately or are divorced or separated. However, the rules for HSA seem to say that you can use the HSA to pay for expenses for children who are your tax dependents, and for children who would have been your tax dependents except for divorce or separation, but there is a very obvious lack of mention of children that you don't claim because you are together, but filing separately for economic reasons. If for some reason you plan to have your wife claim your children as tax dependents when filing separately, you might want to run the situation past a local tax expert.
https://www.irs.gov/publications/p969#en_US_2022_publink1000204083
This answer has been verified for accuracy by an Intuit expert employee
