Yes, assuming the two share a network.
However, you need to reduce the strength of any
firewall on the machine that shares-out.
With Pro you would be best off shutting off simple
sharing (bottom of View tab in Folder Options).
With this off, then you may set permissions (on the
share tab for the share-level access and also in the
security tab for the NTFS filesystem-level access)
to allow only the accounts desired to have access
over the network.
When outside of a domain, each machine only knows
of accounts defined on itself. Hence, when connecting
to the share one will need to provide credentials for an
account on the sharing-out machine that has been granted
access (per above two levels). If an account with the
same name and password exists on both systems this
can make things easier (but less safe).
