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some ISP's will let you "relay" mail through their server even though you are not connected to them. Example: if your mail server is supposed to be smtp.verizon.net and you are at Starbucks on WiFi you may be connected to t-Mobile (not verizon) so your mail doesn't go (if you were set as outgoing server smtp.verizon.net). Your ISP may give you a method to send mail, normally it will be selected as "my server requires authentication" on the outgoing server, and then the authentication may be your full user name@your ISP.com with your password. So while you are connected via T-Mobile, you can still access verizon's smtp server with the authentication. :)
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