Sure!
It was really not that easy... We basically followed the Wiki (
Network Edition: Moving from 32-bit to 64-bit Server - Zimbra :: Wiki). The problem: Just adjusting the passwords in the localconfig.xml file was not enough. After some frustrating hours we tried zmldappasswd with all options to set all ldap passwords (amavis, postfix, etc.) again to the old server values. That fixed it.
Another problem: We had the server running on 4GB RAM with about 50 concurrent users. That brought the server down, it was not responding any more. We then set vm.swappiness to 0 and put 8GB of RAM in. Since then it worked much better. Hope it stays that way, keep my fingers crossed...
The swappiness seems to have a huge impact here.
Good luck!
I don't want to do it again...
But once it is done, all seems better. 64bit memory handling is much better, the server responsiveness might have improved, too.