Hi,
If you have Online-JFS installed, you would use the command
fsadm -o largefiles /tmp
If you don't have online-JFS, then it is advisable to boot the system into single user mode as there is little chance that you can unmount /tmp in multi-user mode. Once /tmp is unmounted, in single user mode, do
#mount /usr
#mount /var
#/usr/sbin/fsadm -F vxfs -o largefiles /dev/vg00/lvol4
#mount /tmp
#init 3
In your case, it is most probably that /tmp (directly under /) is busy so the logical volume is not being able to get mounted.
Try mounting it manually
#mount /dev/vg00/lvol4 /tmp
If it says it's "busy", then you will have to reboot the system to make things clean.
-Sri
You may be disappointed if you fail, but you are doomed if you don't try