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The only way is to find Cynthia (you have probably talked to her by now), and she will give you a Secretpotion. Go use it on the Psyduck, and they will move.

To find Cynthia, go to Pastoria City, and talk to the Grunt outside of the Safari. Follow him until your Rival battles you. Then keep following the Grunt until he battles you also. Once you take out the Galactic Grunt you've been following, Cynthia will come out and talk to you.
You must go to Pastoria City. At the front of the Safari, there will be a Team Galactic Grunt. Talk to him and he will run off, follow him until your rival wants to battle you. After you take out your rival, keep following the Grunt until he battles you as well. Once you defeat him, Cynthia will walk towards you and hand you a spray that makes the Psyduck move. Use it on them then you are free to continue towards Celestic Town.

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Q: How do you move the Psyducks on Pokemon Diamond?
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