You'll have to check the processor on each of your machines to see if they are 32bit or 64bit...doesn't make a difference which version of Windows you are using. Give me just a sec and I'll look to tell you how to find that information.
Ok go to Start > Type: msinfo32.exe under System type you will either see x64 based or x86 based (or possibly 32bit). x64 means you have a 64 bit capable processor. x86 means you have a 32 bit capable processor.
as for the psd file compatibility all you need to do is right click on a psd file > open with > choose program > make sure the box is checked that says Always open this file type with this program (or something of that sort going from memory on the exact wording since my OS is in Dutch) > then choose Adobe Photoshops CS5.
HTH helps
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