Hi @user1293 and welcome to the community. While I am no expert, I have had my old (approx 14 year old) DSCPower864 panel updated with Envisalink in the last two years and integrated with Hubitat. In order to keep with my philosophy of a dedicated, reliable and UL certified purpose built security system for safety reasons, out of my 64 zones, all are hardwired for reliability with the exception of 5 - 6 zones (mailbox and some doors and shock sensors for wiring convenience reasons). Alarm functions are all handled by DSC, with Hubitat only using the sensors (motion etc) for home automation and other convenience functions (non-critical safety/security functions).
Motion response has been virtually instantaneous in most cases and its nice to not have to worry about having additional sensors (especially not battery powered ones that are dependent upon Z-Wave, WiFi or Zigbee, although many here have used Zigbee and Z-wave successfully). At any rate, for the most part, not having to worry about battery status is a plus, as well as too many additional “warts” on the wall and ceilings which affects the WAF. However, remember that Envisalink is quite “chatty” (it can be responsible for 45% or even more of the busy time use according to review of the HE app logs) and so the response can slow down if you have some very resource hungry apps/devices in addition (such as Ecobee thermostats linked to HE, or other devices with frequent polling rates). So YMMV.
Remember that whether you use your DSC sensors for HA or not, the important thing is that they will serve as stand alone security/safety sensors whether your hub goes down or not. If you sensors that are dependent upon the hub (OK for HA but not for security purposes IMHO), then if your hub goes down, so does your essential security/safety system. If you have already planned on using DSC with Envisalink and Hubitat, you can always try the wired sensors for HA purposes and if you find they are not responsive enough for you, to then add in some dedicated sensors for HA that link directly (and locally) with Hubitat (either Zigbee or Z-wave depending upon your preferences).
As I set up my DSC system from the get go myself (got all the programming manuals and equipment when you could purchase everything direct as a end user, now much of the info is “doled” out to distributors and professional installers and is less readily available to the end consumer) I learned the ins and outs of all the different program settings from the professional installer’s manual. Which brings me to your questions about if the sensors work when the system is unarmed. IIRC, there are about 30 or so different attributes as to how a given zone functions. IOW, various zones can be programmed depending on how you set the code for each zone to react differently whether the system is armed in stay or away mode, disarmed, etc, etc, etc. Depending upon the zone attribute settings, you have a tremendous number of options of how you can made each of these zones react when triggered. Due to the complexity, I use the DSC LCD alarm panels as they make programming the system much easier than trying to program it via a LED panel. These attributes or “characteristics” are programmed and set in the DSC panel, Envisalink only tells you if the zone is open or closed (and to answer your question, does so whether your panel is armed or disarmed).
You can use Hubitat to arm the system due to the integration via Envisalink. I use voice commands via Alexa to “arm the house in stay mode” or “arm the house in away mode”. I would not suggest using Hubitat to disarm the system or use voice control to disarm the system for obvious reasons, although it can be done.
I have not utilized Hubitat itself to bypass specific zones when arming. Again, I have the attributes set in DSC itself which allows it to bypass certain zones automatically if they are open or already breached at the time of arming, so I have not had a need to do this via Hubitat.
Ultimately, because of the amazing integration between DSC, Envisalink, Alexa and Hubitat, your ingenuity and imagination are basically your only limits on how you can integrate your system with regards to automation (e.g. setting off any motion sensors or door/window contacts can make verbal announcements to help you identify which sensors have been triggered, and can give verbal warnings and can trigger other deterrence measures such as turning on lights or sprinklers etc, and can vary the response depending upon whether the system is stay or away armed, not armed, time of day or Hubitat mode, day of the week, object recognition with your security camera system, etc and any combination thereof.
Things have come a long way since I started using X10 and Stargate automation over 30 years ago, lol (as well as having got a lot less expensive, versatile and capable too!).
I now have my security camera system (Camect for object recognition), DSC security panel with Envisalink, automation system via Hubitat, and voice control and announcements all linked with Hubitat in the middle controlling automation functions, and DSC running security/safety/fire/CO even if Hubitat goes offline (it is not recommended nor endorsed by the HE staff to rely on Hubitat for essential safety functions).
Anyway, welcome to the fun! Hope this helps a little.