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To be able to wake up a PC, it may be powered off or hibernating, usually it doesn't make a difference.

The requirements for WOL are:

• BIOS supporting this feature,
• The motherboard must have a special connetor for WOL,
• The network card has to be connected with a cable to the WOL connection on the mobo,
• the PSU must supply enough current so the network card is still working when the computer is turned off (in a lower power mode, but working).

With all this there are programs that using the MAC address can send the magic packet that will wake up the computer.