Zoned heating system from disparate line-voltage and low-voltage thermostats

Most of what you are asking for is easily accomplished using Hubitat's modes and Rule Machine once you get smart thermostats installed. The exception may be controlling Hubitat's mode from the thermostat. Although some thermostat's have the concept of various modes like home, away, sleeping, etc., that information is not part of what is typically communicated to Hubitat.

Most of this should be doable with a smart door lock and smart light. I don't think any of the smart locks distinguish between locking from the outside and locking from the inside. I've heard mixed results distinguishing between manual locking events and Hubitat commanded locking events.

I am not familiar with line voltage system like what you are describing, so I will not comment on that aspect.

Based on this description, you should not assume that any smart low voltage thermostat will work as a simple replacement for what you have. Two wires wouldn't usually be sufficient for both power and signal, unless some non-standard protocol is used. Is the thermostat battery powered? Is it an old-fashioned thermostat that doesn't need power? I recommend that you investigate how this is wired and hopefully physically find the relay that you suspect is there. You may end up wanting to run 5-conductor thermostat wire to the thermostat. Alternatively, you may end up deciding to replace that relay with a smart relay like a Zooz ZEN16 and not rely on the wire to transmit the signal. (That option would make your system dependent on your Hubitat for basic function.)