New computer, old .mac account, can't send e-mails!

A friend gave us his old Titanium PowerBook G4. We have an iBook G3 that we've been using and I'm trying to set up the new/old PB for my wife as her personal computer.
I upgraded osx on the pb and then tried to configure e-mail for my wife's account. I copied all of the info. exactly as it is in her old account on the ibook. For some reason, it will not send e-mails, though it will recieve them.
When I try to send e-mails, I get this error:
"Use the pop-up menu below to try a different outgoing mail server. All messages will use this server until you quit Mail or change your network settings."
I switched the port number from 25 to the recommended one and also double-checked that everthing was copied correctly. But we still can't send mail from her computer. I couldn't find the answer with searches... any thoughts? Thanks!

Thanks!
Here's what the error message is:
Cannot send message using the server
smtp.mac.com:wifes.address
Use the pop-up menu below to try a different outgoing mail server. All messages will use this server until you quit Mail or change your network settings.
Message from: Wife's Name <[email protected]>
Send message using: smtp.mac.com:wifes.address
So, I'm not sure what to do from here. I've tried various port addresses and none work. All that happens when I try to send a message is that I get the above error and the draft goes into the outbox.
Thanks in advance for any help, this has been really vexing for us and I'd love to get my wife up and running.

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I hope someone can help since even the Mac Genius at the Apple Store nor Applecare seem to know.
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Did you place a copy of the entire Mail folder located at Home > Library > Mail on the Desktop?
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