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Let me explain something, this goes for any internet connection...
If you dialup/connect with ABC provider (insert method here) and then wish to send email from your email account with provider XYZ, then of course the incoming mail server (POP or IMAP) would be the set to the provider XYZ, but to send email you MUST use the outgoing mail server of the provider your currently connected too for that internet connection.
So in this situation, you must use ABC provider's outgoing mail server to send mail (SMTP server).
Basically all mail servers are configured this way to avoid them being configured to RELAY mail for anyone. They will only RELAY mail for people/customers on IP addresses the ISP owns (not people on another ISP's ip address). Otherwise anyone could abuse the mail server and not be a customer. It's to stop abuse and spamming. OPEN RELAY smtp mail servers = BAD!
It's simple as, when connected to ABC providers network, you must use ABC providers SMTP server for outgoing mail, when connected to XYZ providers network you must use XYZ providers SMTP server for outgoing mail.
Hope they helps you understand a little better.
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