According to this post - YES you can.
The following declaration will generate 2 indexes:
DECLARE @Users TABLE
(
UserID INT PRIMARY KEY,
UserName VARCHAR(50),
FirstName VARCHAR(50),
UNIQUE (UserName,UserID)
)
The first index will be clustered, and will include the primary key.
The second index will be non clustered and will include the the columns listed in the unique constraint.
Here is another post, showing how to force the query optimizer to use the indexes generated dynamically, because it will tend to ignore them (the indexes will be generated after the execution plan is evaluated)