I believe it is  in the pref, accounts and there you can set the smtp server. 
alternatively you can go to 
/Users/username/Library/Mail/V2 and delete the folders 
[email protected]
Mailboxes
MailData

You will have to recreate the account but I've found this worked when I was 
having some issues.
On Jan 13, 2012, at 8:19 AM, Sunil Peck wrote:

> Hi,
> 
> Is there a way to restore the default settings for a Googlemail account in 
> Mail? I'm unable to send any emails at the moment, when VoiceOver reads out 
> the SMTP server when I navigate through the fields while composing an email, 
> it says that my SMTP server is offline. I don't know what that means and 
> can't find an option anywhere to restore the proper settings.
> 
> Thanks a lot,
> Sunil
> 
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