for List explicitly yes it should be private depending on what the functionality you're exposing is supposed to do, interfaces such as IEnuemerable, ICollection or IList would be a better choice or if you're exposing a collection See SLaks reply.
Generally exposing internal structure and state is a bad idea and since your object of type List is both, you would want to keep it internal.
It might make sense to give the user the ability to iterate over it, to add or remove items to it but you should still keep the List internal and either expose Add/Remove methods or as a minimum expose an interface making it possible to change the type of the internal representation with out affecting the public interface.
Further more if you are exposing using an interface you should go for the narrowst possible interface.
So if the client code only needs to enumerate it. use IEnumerable if client code needs to index use ICollection and so forth.
further if you expose as an IEnumerable you should make sure that what ever you return is in fact read only by either using a read only collection class or by use of an iterator block
EDIT after update
In regards to your example. Ask yourself does it make sense that any one except the Employer can change who his employees are? to me that's in the words you've chosen already. The Employer employs the Employee and should have full control over who his/hers employees are. So it that particular case I'd keep it private and expose Hire(IEmployee employee) and Fire(IEMployee employee) that why the code plainly states the intent