As many of you know, the email servers at Stanford will only accept encrypted connections, starting June 24th, 2010.
I use postfix extensively. This is what I did in order to enable TLS connections:
Edit main.cf and add the following two lines:
smtp_tls_security_level = encrypt
smtp_use_tls=yes
These will force all outgoing connections to be made exclusively through TLS.
This works well because I use Stanford SMTP servers as my smart relay (see relayhost option). If you relay directly to other destinations, then you might want to use smtpd_tls_per_site instead.
To debug the connections, use the following:
debug_peer_list = stanford.edu
debug_peer_level = 2
And then check your log files. Make sure to disable them later (just put a # in front of them) to avoid filling up your logs too quickly.