AppleCider
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The trick here is to be sure you have a layer filled with your foreground color (don't ask me why, but at least in PS 6 this only works with a layer completely filled with the foreground color) Then, with that layer active, activate your rulers. Be sure "Snap" is checked under the View menu. Drag a horizontal guide from the top ruler; it will snap to the center of the document. Do the same with a vertical guide; it will also snap to the center.