That's quite easy to do.
For legacy postbits, in template postbit_legacy find:
Code:
$post[iplogged]
Add after:
Code:
<if condition="$post[userid] != $bbuserinfo[userid]"><if condition="$show['pmlink']"><a href="private.php?$session[sessionurl]do=newpm&u=$post[userid]" target="_blank" rel="nofollow"><img src="$stylevar[imgdir_button]/pmimage.gif" alt="pmimage.gif" title="<phrase 1="$post[username]">$vbphrase[send_private_message_to_x]</phrase>" border="0" /></a></if></if>
Then take the image you want to use, call it pmimage.gif, and upload it to your /images/buttons folder for each style.
This will display a PM link that opens in a new window (remove target="_blank" to make it open in the same window). It also should only show the button to members, and should not show it in your own posts as you wouldn't normally PM yourself!
For standard postbits the same code can be used, and I imagine it could go in the same place, but I don't use standard postbits so I can't check. But instead of editing the template 'postbit_legacy', edit the template 'postbit'.