SQL Server 2008R2 XML Column Index strategy for large tables?
You should have a look at Property Promotion in XML Best Practices for Microsoft SQL Server 2005.

Create a user defined scalar valued function that extracts the value you need and use the function as a computed column in your table. You can persist the column of you like and you can create a regular index on the column. You don't have to persist the column in order to create the index.