How does the vCPU align with the CPU? (VM with more cores than the CPU has)

A single VM must never have more virtual CPUs than logical physical cores that are available.

With Hyperthreading enabled you are at 44 logical physical cores, so this should be fine. However, this heavily depends on how many more VMs are running on that host. One thing you have to keep in mind is how the CPU scheduler of the ESXi server works. For every CPU cycle it always waits until there is a physical core available for each virtual CPU on a VM. So, in your case, it will always wait until 22 physical cores are available before a CPU cycle can be processed. If you have many more VMs on that host that can lead to a high CPU ready time and a very slow VM.

Personally, I always try to keep the number of vCPUs at 8 or less. If you can, rather scale your VMs out than up.

Another consideration: With the current state of mitigations against Spectre and Meltdown attacks it is generally recommended to disable Hyperthreading, because this reduces the possible attack vectors. If you decide to disable Hyperthreading your configuration will most probably not be usable anymore.

I can't think of a situation where you'd want a single VM to have more vCPUs allocated than there are physical cores in a server.

Benchmark your workload with the current VM configuration, and then see what happens as you gradually lower the number of vCPUs. Take note both of execution speed for your workload and of actual CPU usage on the host/VM from the hypervisor's perspective rather than that of the guest OS.

Usually when setting up VMs it's beneficial to start with a rather low number of vCPUs and then working your way up until the performance increase flattens out. For many workloads you don't necessarily need to stick to even numbers of vCPUs, even though there are exceptions to this principle. Again, a good test run should show how your application deals with its environment.