Most ISPs that provide cable connections block port 25 to counter spam. Instead, they provide you with their own outgoing e-mail server to send out e-mails. You need to specify this e-mail server in WebCam Monitor. To do so, click "Configure SMTP Server" on the E-mail Notification Alert settings screen.
If you have Outlook configured correctly then you can refer to these settings.
Also, make sure that you using the latest version of WebCam Monitor. To download the latest version, visit:
/wcm