NetHunt users are physical email addresses.
When a user is invited to a workspace - they need to accept the invitation. Thus, you cannot log in under an alias and use the system.
If you want to only send emails from another email address WITHOUT adding the alias to the workspace, you can use the SEND AS feature that will allow you to use that address both in single emails or email campaigns. This is a purely Gmail feature.
To set it up check this guide.
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