The one thing you will have to make sure of is that the drive letters for the partitions on the new drive match the old drive letters. I would also take a backup of the Exchange server before starting and then set the Exchange structure to an unsecure state. This is done in the Admin and you remove ALL the accounts from the permissions pages for the three level containers (Org, Site & Config).
This way should a problem occur Exchange can be started by any account that can logon to the server.
Something to consider is that Exchange performs better if the database files and the transaction log files are on separate drive spindles rather than different partitions of the same drive spindle.
One very important point would be to plan for worst case scenario (Drive Ghosted the wrong way).
Checklist:
Make sure your MB will support a 40G drive
Make sure you running SP6a (Assuming your OS is NT4)
Do you have enough drive bays in the exchange server case to add the new additional drive? If so, you can add the additional drive (IDE or Scsi) format the drive, then run the Exchange performance optimizer which will determine the best location for the databases, and log files, etc and can make the changes for you, eg: will stop and start the services and move the database files for you. Note: always perform and good backup before and after doing any major tasks on your servers. (Not ususally needed, but better safe than sorry.)
Try reading the following articles from microsoft. Perf OPT is a really good tool for managing your servers databases and drive space allocation.
XADM: Rerunning Performance Optimizer Is Recommended After Applying Service Pack (Q271824)
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