How to create RTF files in A4 format by default?

DEVONthink doesn’t specify a paper format on its own. I just created an empty RTF document and had a look at the RTF code created by macOS and it doesn’t seem to include a paper format either.

But you could add a template to the folder ~/Library/Application Support/DEVONthink Pro 2/Templates.noindex and use the template to create new documents.