I'm doing it that very way now. Easiest way is to make an empty folder within C:\Program Files or C:\Program Files (x86) if you have a 64-bit machine and name it Virtual PC.
On your Caviar Black, make a partition of whatever size you deem necessary for the XP mode install--20, 50, 100GB (?)--whatever is good for you. Name the partition XP Mode.
After making that partition, open Control Panel > Administrative Tools > Computer Management > Disk Management. Right click the newly created partition, XP Mode, and select Change Drive Letter and Paths. Click Remove, then OK. Again, right click the XP Mode partition and select Change Drive Letter and Paths. Click Add. Check Mount in the following empty NTFS folder, click Browse, and find the folder you created named Virtual PC. Click OK.
So when you download and install Virtual PC/XPMode, make sure you point the installation to that folder--C:\Program Files\Virtual PC or C:\Program Files (x86)\Virtual PC and the operating system will recognize the installation as being installed in C:\Program Files... but the files will actually reside on the HDD.
Hope that wasn't too confusing.