Most often this problem occurs when your internet service provider (ISP) blocks their sending port from use by other servers.
Example: If your internet service provider is bellsouth for example and your outgoing mail server is set to mail.yahoo.com or smtp.yahoo.com or mail.yourdomainname.com etc.... it may be getting blocked by bellsouth. The do this to avoid spammers from using their systems.
To fix it, contact your internet service provider and ask what your outgoing mail server should be. For Bellsouth it would be mail.bellsouth.net. Replace your outgoing mail server information with the information provided by your ISP and all should work well.
Here is the link to Microsofts step by step instructions on changing this information in Outlook
Express:
http://www.microsoft.com/windows/IE/community/columns/mailserver.mspx
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