Outgoing mail server failure

Can't send email using Apple Mail. I've set up dozens of accounts so I know my settings are correct. Within a few seconds of sending a message the "Can't connect to the outgoing server" box pops up on the screen.
Could this be a corrupted file? Which one?
Thanks.

Ernie,
Thank you. I have checked and they all appear to be mapped correctly although I do notice whilst that the account information email address box shows both the .mac and the .me version when I go to 'edit SMTP' list it doesn't show the .mac server as being in use by my .mac account (it doesn't show any account). The .me version has in use by my account. Could this be part of the problem and if so what should I try doing. Thanks for you help by the way.
Roger

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