Yes, but unless she has other income her entire salary is at lower rate. If she's just started work it's unlikely she'll pay any income tax in 2023 as her PAYE credit will cover tax on the first 8,875. Her tax will be a bit messy this year if you were claiming a homemakers credit up until now.
Have a look in the public sector pensions forum. There's lots of advice for late entrants to the public sector, and discussion on fees for AVCs.