This week's book giveaway is in the OCMJEA forum. We're giving away four copies of OCM Java EE 6 Enterprise Architect Exam Guide and have Paul Allen & Joseph Bambara on-line! See this thread for details.
The answer may be yes, sort of. Outlook can be controlled by external programs like that, I used to have a Visual Basic program which did it.
But versions of Outlook since 2003 have had the security feature where when an external program calls Outlook's send-mail feature, it waits until the person sitting at the screen confirms that it's okay to do that.
Frankly it would be easier to use JavaMail. If you can configure Outlook with the address of the mail server, you can certainly configure your application with the same address. I would invest more time in looking at that simple option rather than being dead-set on the horribly complex Outlook-driving option.