Although Devolutions' PAM capabilities are usually managed at the vault or system level, they can also be leveraged for specific session entries in a few clicks. Here is how:
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Click on the Properties (pencil icon) of your chosen entry.
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Under Common – General, click on the Credentials dropdown menu and select Privileged account.

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Select a previously created privileged account (a PAM entry linked to a PAM provider) from the list. Click Update.
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Click Open session in the dashboard.