Are you shutting down all non-essential programs (especially anti-virus) before starting the game? Firewalls can cause conflicts (generally on startup or loading screens) and overlays from graphics tweaking/monitoring programs or chat programs can also caused issues.
Try doing a clean boot and then test the game. For example, there is a known conflict with the Nahimic service used by two audio programs (SonicRadar and Sonic Studio) for certain motherboards which can cause the DE to crash after about a second of black screen, but the Classic release is ok. In that case, there may or may not be an event listed in the Event Viewer for NahimicService.exe, as well as the game executable (probably both 'RADAR_PRE_LEAK_64' events); this should be fixed with the latest updates for the Nahimic drivers and apps.
Click Start, or hit WinKey-R, type in msconfig and hit enter; in the General tab, click Selective Startup, uncheck Load startup items (if required) and leave Load system services and Use original boot configuration options checked. Next, click on the Services tab, check the box to Hide all Microsoft services, then click the Disable All button (maybe make a note of which are currently enabled/disabled), then click OK and reboot the computer.
Run msconfig again to switch back to the normal boot configuration.
Try changing the default audio output in Windows. A handful of people have reported crashes in the DE, but not Classic, that could be avoided that way (or in a couple cases fixed by changing, starting the game, exiting and switching back), some related to USB headsets.
Try browsing to the '..\Documents\Larian Studios' folder and rename the 'Divinity Original Sin 2 Definitive Edition' folder again, and try
this replacement folder.
If that doesn't help, please email supportdos2@larian.com with a dxdiag report (WinKey-R, type in dxdiag and hit enter, then when it finishes loading click on the 'Save All Information...' button and save the report somewhere handy) and a link to this topic, and zip a few of the 'CrashDump' files together to include.