There are a few different questions going on here.
- Mutational clocks are not the only, or even the primary, means of dating specimens of these species. More common is to use carbon dating, for example as done here, to establish when certain species existed.
- Mutational molecular clocks are calibrated based on observed mutation rates. It is fairly routine to measure mutation rates per generation using whole-genome DNA sequencing. We have a good vision of what substitution rates are on average throughout the genome.
For an intuition of why this works, consider that there are roughly $3*10^9$ bp in a haploid human genome. The human mutation rate is about $1*10^{-8}$ per generation. So every generation, we expect around ~30 new mutations on average per haploid genome. It's simply a matter of observing the whole genome to find them.
Mitochondrial genome mutation rates are quite a bit faster, and were some of the first genomic regions used to do this kind of dating, before whole genome sequencing became so routine.
Using that kind of information, we can make some statistical guesses about the relationships between Homo species (I'll let you look at some of those references to see how that is done).