I have the following SQL command:
ALTER TABLE dbo.UserProfiles ADD ChatId UniqueIdentifier NOT NULL, UNIQUE(ChatId), CONSTRAINT \"ChatId_default\" SET DEFAUL
Don't use newid() as default, instead use newsequentialid(). newid() creates a lot of fragmentation and that's bad for indexes.
newid()
As far as adding the new column to a table with existing data, simply do this:
ALTER TABLE your_table ADD your_column UNIQUEIDENTIFIER DEFAULT newsequentialid() NOT null