I have version 2.64. I am notified via email when comments are made to a post. However, I don't believe that the folks on my notification list are being emailed (I am one of them) when I publish a new post.

I have checked my weblog config etc. everything seems to be fine.

What else can I do to resolve this?

After you publish the entry, are you scrolling down on the Edit Entry screen and sending the notification from the relevant area of that screen? It's not an automatic thing, it has to be sent manually.