I see no reason why you shouldn't do this, though you should certainly test it for yourself 😀

I wonder why the currently installed SQL Servers are 2000 Standard - I would have expected MSDE...?

One common 'gotcha' with Express versions: there is no SQL Server Agent.

Also look into SQL Server Compact 3.5 - it seems a better fit than Express, on the face of it.

But yes, have a chat to your Microsoft TAM or whatever.

Paul