Here is a little Magento extension I wrote recently, its called Inchoo_AdminOrderNotifier. The whole idea behind the extension was to fulfil the request where you as a merchant wish to have your store personel instantly notified when customer places an order on your store.
The way extension works is that it observes the sales_order_place_after event, and then triggers the code that sends the special transactional email called Inchoo Admin Order Notifier. By default this email is almost indentical to the built in New Order transactional email. Its up to you as a merchant (Magento admin) to modify this transactional email to suite your needs (System > Transactional Emails > Add New Template > Load Default Template > Template > Inchoo Admin Order Notifier).
Extension supports several configuration options, which can be accessed via System > Configuration > Sales > Sales > Admin Order Notifier, as shown in the screenshot below.
Magento 1.9：新订单通知 Admin Order Notifier
Please note that by default Magento does have Send Order Email Copy To option, available under System > Configuration > Sales > Sales Emails > Order section, that even accepts comma separated list of emails. However the main difference between that option and the option you get with this extension is that this extension supports special transactional email just for the notification, so you might fully edit it prior to notifying your personel.
