the PS-5 it is very legal with expression pedal... but if you want a whammy catches one... Joe Satriani uses the two in his board and it also uses an octave BOSS...I think has place for the two in the board... the PS-5 doesn't have like you to change the function during.
The PS-5 wouldn't be as easy to control, nor would the transition of sound be as smooth as the whammy (you'd probably get a series of steps through pitch rather than a smooth shift - ie like running your finger up a fretted bass as opposed to a fretless). The PS-5 is really more the successor to the HR-2 and does its best work as a harmonist.
I don't have a Digi whammy, but from what I've heard thaey are pretty damn good at what they do - think Tom Morello of Rage Against The Machine. I've also heard that nothing else really compares (possibly all biased views). I will try my PS-5 with an expression pedal and get back to you (I doubt it will sound so good - the PS-3 doesn't when used in this way).
There is nothing like the WH-1 of Gilmour, Dimebag, and Morello fame. Some people here have them. Another way is the Digitech IPS-33b which is supposed to have the WH-1 circuitry - however for whammy you'd need to do midi control..and they're over half the price of a vintage WH-1 anyway.
but
The PS-5 with an expression pedal approaches the sound of the current Digitech Whammy (4), but isn't quite as smooth (as natthu suggested) to my ear.. if you fiddled around enough with it and got used to the sweep etc, you'd probably be able to pull off most of the sounds you're thinking of.. A good music shop should let you try the combo out in the store. A comp in front of the PS-5 might help as well..
I was also interested in a whammy a while back and was looking at the PS-5 as a possibility as you have the harmonist function as well so you could have a double whammy in one pedal(sorry couldn't resist..)..but the consensus was it wasn't up to the digitech for the gilmouresque type stuff...i also heard/read (i think it was a review or comment by Dirk) that the newer whammy reissue wasn't great either and nowhere near the original.....so i didn't have/wasn't interested in spending a small fortune on Ebay after an original..........left this one to the famous.."i find it in a pawn shop or car boot sale one day".....