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iMule is a Peer to peer application, and in order to enter the peers network, it has to know at least one other iMule peer on start. The known peers are kept in a file named "nodes.dat" in iMule's configuration directory. On first use, you can copy the file provided in the archive into the configuration directory. You can also click the "Nodes" button in iMule to try to download a more recent nodes.dat file from iMule's website, but before doing so, you have to wait until iMule says it has successfully connected to the I2P network.
The remaining of this document has been pasted from aMule documentation and are more or less relevant for iMule (I did not check everything).