Given the following section in Web.Config:
this is a configuration that worked perfectly for me:
there is no way to add the SSL parameter to the network tag. You will have to set it from code:
var smtpClient = new SmtpClient();
smtpClient.EnableSsl = true;
smtpClient.Send(message);
If you don't want to send the emails out using an external smtp, you can configure it to use the localhost and use a desktop email receiver like PaperCut (http://papercut.codeplex.com/). This is the config to achieve that:
Hope this helps!