Inviting collaborators happens in the Settings module. Here, in the My structure section, click on the Collaborators box.
You'll see a section where you have (or will have) a list of your collaborators.
By clicking on the blue “Invite collaborators” button, a window will pop up where you enter your colleague's email and optionally add a note.
The person will get an invitation in their inbox, and once they accept, they’ll be added to your structure (it doesn’t matter if they already have a FreshFlow account or not).