You can use Javascript to make a secondary HTTP request before submitting, but you will need a server-side script (Perl, PHP, ASP, etc) to send the email.
There are a number of ways to make that request in Javascript - you may want to look into an AJAX call or setting the src property of a hidden iframe.
Unless this is purely an information email, along the lines of "Someone might be buying these items" or "Survey results from recent purchase", I would caution you against doing this. There is no way to tell whether the person paid for the item (they may very well go to PayPal and close the browser window). If you have a high sales volume it would be very difficult to match payments with whatever important information is in this email.
PayPal offers "Instant Payment Notification" or IPN which allows you to specify a script on your site for PayPal to notify when the transaction is complete and the payment is received. Then you have the PayPal transaction id, cost, amount paid, and additional information if necessary. PayPal provides several shells in various languages which do the proper necessary authentication steps to make sure that the transaction is real and not spoofed. You would just add code to one of those shells that sends your email, now able to say "So-and-so bought these items, prepare to ship them.