Dual network connections

I want to decouple the esphome and other smart switch devices from my normal wifi system. Is it possible to configure homeassistant to use a separate wifi connection from communications with those devices. What I have in mind is to continue to use Ethernet to connect my front end devices to homeassistant and add a wifi usb device to talk to a separate router with a new, different ssid.

If you are good at networking, all things are possible.
However HA is designed and works best with a flat network, where HA and all its interfaces are on the same network segment.

And to be more precise.
Good at TCP/IP v4 and TCP/IP v6 and understand the difference between unicast, multicast and broadcast, and how routing is possible and not possible with these types of packets.
Then you need to understand each of the protocols every device you have use and what needs to be routed and then hat does not.
And lastly to also need to understand how services are bound to a network and what limitations there can be in binding services to multiple networks.

Many think “Good at TCP/IP v4” is enough, but the rest is just as essential for a basic working setup with multiple networks. We are not even talking advanced setup for multiple LANs here.

I use a separate firewalled VLAN for my IoT network that houses Home Assistant.

You are using the only simple setup with multiple LANs, which is having HA and all IoT devices in the same LAN and then letting the router handle the routing of the few protocols from other places.
The GUI (and the companion apps) are just HTTP or HTTPS requests, so they are easily handled.

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It turns out that the networking was straight forward. Both HAOS and my linux laptop now have two wifi adapters, one tied to each network. My private network needed internet access only long enough to setup the router and for configuring a couple of TP-Link switches.
Moving the esphome devices from one network to the other took some thought. OTA through the web server was the most straight forward way of getting them there.