I am not at all surprised that using 16 cores on one node with OpenMP is faster than using 16 cores spread across 4 different computers (nodes). The 16 cores on a single node are usually part of the same "chip" and are definitely attached to the same motherboard. The 16 cores spread across 4 computers will not be able to communicate with each other nearly as quickly as if they were in the same chip or on the same motherboard.
Is it possible to accelerate such calculations?
Since for this calculation, OpenMP on a single node gave the fastest results out of the three experiments you did, to acceleration your results, I suggest you try to use more OpenMP cores on a single node (I would be surprised if your HPC cluster has nodes with only 16 cores, because for the last several years, most HPC nodes have 24, 32, or 40 cores.
If you still want faster results, you can add a second node. This will allow you to double your total number of cores, but please do not expect the speed to be twice as fast as when you used 1 node, because there can be overhead due to the fact that you are now using two separate computers with two separate motherboards (connected by Omni-Path, or InfiniBand, or even an Ethernet cable in some rare cases!). If you have two calculations like this to do, I recommend that you run each of them on a separate node with maximum OpenMP parallelization, rather than to run one calculation on two nodes, and then the other calculation on the same two nodes.
So when should you use MPI? Two examples of when I'd recommend MPI are:
When a single node does not have enough RAM for the calculation, you can use "distributed memory" meaning that data needed for the calculation can be spread across multiple nodes to give you sufficient RAM to store all the required data. This is probably not your case, because while 462 spatial orbitals is a fairly large amount, the integrals will indeed be manageable on a single node on most HPC cluster built any time in the last several years.
When the algorithm you are using is "embarrassingly parallel", meaning that there is essentially no communication needed between the nodes, so doubling the number of nodes will in fact nearly double the overall speed of the calculation. This is the case for FCIQMC, but not so much for the SCF in DFT (which is what you're doing, and is probably why your use of MPI is slowing you down in comparison to using OpenMP with the same number of total cores).