There's two distinct things, here. Firstly, as Michael notes, depending on the Notification settings, the person a content object is assigned to can receive an email notification when that assignment is made. So you can set the Status for a content object to (e.g.) Ready for Review, and set the Assign To to John Doe, and John Doe will receive a notification. You don't need to use a 'Workflow Process' (capitalized to identify it as a specific thing) to do this. This is what you will probably do when you assign a content object to a SME - use Assign To and they'll get the notification. But again, you don't need a Workflow Process for this.
The second thing is the actual Workflow Process itself. These are defined in Manager, and can be automatically assigned to content objects created within the Workarea. The Workflow Process controls what statuses a content object can have, in what order, and who can advance the object from one status to the next. One of the other things you can do is define 'Watchers' to a specific 'transition' (from one Status to the next). So, for example, you can say "always notify John Doe every time the status of a content object goes from In Progress to Ready for Review.
However, there is a limitation in that you can only identify individual users as Watchers. You cannot define a Role as a Watcher (for example, to say 'inform all Master Authors when the status of a content object changes to Ready for Review'). You can assign multiple Watchers - or even a dummy User that is actually the email address of a Shared Mailbox, but this would consume a license. (There is a Customer Improvement Request to allow assignment of objects (and Watchers) to a Role or OU.)
The other problem with Watchers is that 'anyone who ever touches a content object' will be recorded as a Watcher for that content object. And once you're a Watcher, you will always get the notifications - even if the object is no longer assigned to you. You can remove Watchers from an object, but only from Manager. And you cannot remove the original creator (again, there's an Improvement Request in for this).
My guess is you are not using an actual Workflow Process. (And don't be fooled by the Change Workflow option in Producer - that is not exclusive to Workflow Processes. If you do want to use Workflow (which, honestly, is not necessary just to assign objects to SMEs and then back to Standard Authors), like Michael says, it's probably best to get in an "experienced SAP Consultant". Like me. 🙂
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