The purist (I try to stay pure) will tell you that your model represents your data. And therefore, anything that needs to be persisted is done so only when needed through repositories. Also, when you have complex entities, you want to use a service to combine them. For example, User + Employee = UserEmployee entity that is only accessible through an IUserEmployeeService.
With those vague statements, you have an excellent opportunity here.
Build an anti-corruption layer, which allows you to start moving off of the legacy DB at the same time.
This is an another chapter in the DDD playbook. An Anti-Corruption layer is used to interface with a legacy system using Facades, Translators, and Adapters to isolate the legacy DB with your pure Domain model.
Now, this may be a lot more work than you wanted. So, you have to ask yourself at this point:
Do I want to start the process of
moving off of this legacy DB, or will
it remain for the life of the
application?
If your answer is you can start migrating, then model your actual domain the way you want it. Persist it with normal repositories and services. Have fun designing it the way YOU want it stored. Then, use the services of the aggregate roots to reach into the anti-corruption layer and pull out the entities, store/update them locally, and translate into your domain's entities.
If the answer is that the legacy DB will remain for the life of the project, then your task is much easier. Use your domain's services (e.g. UserEmployeeService) to reach into the anti-corruption's UserFacade and EmployeeFacade (similar to a "Remote Service" concept).
Within the Facades, access the legacy db using the Adapters (e.g. LegacyDbSqlDatabase) to get a raw legacyUser(). The next step would be to use an UserTranslator() and EmployeeTranslator() mapper that converts the legacy user data into your actual domain's version of the User() entity, and return it from the UserFacade back to your UserEmployeeService, where it is combined with the Employee entity that came from the same place.
Whoa, that was a lot of typing...
With your Adapters and Facades of your Anti-Corruption layer, you can do your Linq-to-Sql or whatever you want to do. It doesn't matter because you have completely isolated the legacy DB/system away from your nice and pure Domain - your domain that has its own version of User() and Employee() entities and value objects.