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From the Definitive Guide to Plone [plone.org] (PDF, p. 77):
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4.1.2.2 Setting Up a Mail Server
Plone will send e-mail using the MailHost object, which provides an interface to an SMTP server and allows the developer to write forms and tools that send e-mails. The ’send-to-afriend” function and the mailing of a forgotten password use the settings configured here. The default configuration is for a mail server on the localhost at port 25. If the SMTP server is located elsewhere in the network, then you can access the form by clicking plone setup and then
clicking Mail Settings. Then change the mail server and the port to suit your configuration. On my network, the mail server is at monty.clearwind.ca on port 1025, so I set the server as shown in Figure 4-4; however, in most cases, you won’t need to change this.
If you already know that and that's no help, these plone smtp config notes might help, though they are host-specific, it might give you some avenues of investigation.
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