Toby,
Your question is vague and I'm not sure i understand it fully, but i will try respond as best i can, and maybe you can expand a little
By saying you would like 'them' to validate emails themselves - this being your clients ? for the sake of the response, I'll assume that you mean clients.
Firstly validating - if full / over quota - is not easy unless you are directly manipulating mail headers and have another daemon running to capture bounces and record erroneous accounts.
You should assume that the links are up to the server and even if the link is temporarily down - a good SMTP server (your side) should keep the mail in queue and retry for a good few hours before finally failing.
Validating a mail addie should not just be that the remote server accepted the mail, a human response is the validating factor and should be required to authenticate that account as valid and that the person there is your intended recipient.
So what i suggest is mailing your client list (XLS, CSV, Database...) with a mail explaining that you are wanting to validate your database of records and could they please
click this link to validate that they received the mail. This link should be a hyperlink to the company website or hosted somewhere and just record that that person is alive and "thanks for validating your email." Hosting this page on the company website will keep the whole process looking legit and not some Phishing attempt.
Another concern would be just making sure your mail server complies with all the necessary DNS requirements such as having a valid host name and reverse DNS set up. Is not an open relay and all the correct ports are open for traffic. Most remote mail servers will not accept mail unless it comes from a FQDN with reverse DNS lookups. Checks out with all the blacklists on the net. The remote server will also attempt to connect back to sending machine to validate things before allowing delivery (not all mail servers).
By running your mail server from behind a firewall you will be NAT'ing the connections through and if you haven't already set this up, it can be tricky.
I also highly recommend using standard mail-daemon software for any task and not some mail bomber, and would recommend an open source option such as Qmail or Sendmail running on BSD or Linux.
Let me add that applications bombing mail servers with mails addressed to people that either do or don't exist to test if the mail is accepted or not is SPAM and you'll find yourself blacklisted and possibly arrested if it is serious.
Hope some of this helps, if you want me to get specific on anything give me a shout.