Another sending mail in Mountain Lion issue

Here's a strange one. My setup:
Mac Mail under OS X 10.8.2
Hard wired to an AEBS (i.e. not wireless)
2 users on the same machine
Each has an iCloud and a Gmail account. The accounts were set up from the Mail preferences pane (so the only info provided/required was the username and password.
Here is the problem:
User 1: everything works as it should. I can send and receive email from and to both accounts.
User 2: cannot send email from the iCloud account. Everything else works.
The test email contains text only.
Here's the dialogue that pops up when trying to send mail from the User 2 iCloud account:
So it looks like it is trying to use the correct account. I deleted and then set up the iCloud account afresh. No change.
Can somebody please suggest how I might begin to diagnose this problem? There are plenty of similar sounding threads, but the prevalent solution is to amend the MTU size in wireless networks. I am hardwired and OS X has negotiated (or been given) a standard MTU of 1500. Thanks.

Yes!

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