Where did you learn that they are using DMR and not some other mode?
How do you know it isn't really a PTT app on a cellular carrier or FirstNet?
How you you know you were not fed BS and believed it?
Which specific law enforcement agency are you trying to find unpublished frequencies for and what system does the agency normally use?
You need to determine that first.
If they are really using radios (DMR or any other) on "secret" frequencies it could be:
1) Existing licensed frequencies that aren't in RRDB. Check all FCC licenses for the city or county in question. Not all of them are in RRDB. They could be using frequencies licensed to one of their neighbors, their county or maybe their state. Federal VHF/UHF interop and 700 MHz interop frequencies might be a place to hide.
2) Leasing air time on a commercial SMR system. You will have to search them individually and not all commercial trunked systems are in the RRDB.
3) Leasing
Part 22 Paging frequencies. Search those.
Least likely but still possible:
4) Illegally using frequencies that somebody pulled out or their @$$ and programmed in the radios like marine, amateur, FRS, MURS, broadcast auxiliary, UHF TV, federal government, or anything between 136-174, 380-512, 769-869 MHz depending on the frequency range of the equipment used.