Instead of NFS, look at iSCSI. It actually works now, has less overhead and fully supports mmap and proper locking. I would recommend investing in a SAN like LeftHand, Equallogic, Compellent, Pinnacle but you could try OpenFiler or the iSCSI target now available as a "technology preview" in RHEL 5.2/CentOS.
Don't rule out FC for cost reasons -- used 2G gear can be found with better price/performance/stability than 10G iSCSI.
RAID5 can be OK for /opt/zimbra/store, but you definitely want RAID10 for data/db/index. A modern thin-provisioned, dynamic-block-migrating SAN can eliminate the distinction and cost less than a build-your-own OpenFiler if you take thin provisioning into account. We happily use Compellents, transparently mixing RAID5 and RAID10 in the same volume.
Yes, various people have used vmware, though maybe not at the 100K user level, and Brandeis is in process of migrating 9K users to ZCS5 on RHEL5 on hand-compiled Xen 3.2. Given the speed with which a VM can live-migrate or fail-reboot, I don't see much point in RHEL or Veritas clustering.
AFAIK, Zimbra clustering package doesn't do anything magical to preserve sessions in progress.