The numerator tells us how often we observed the two words together (assuming we compute probability by using the MLE). The denominator tells us how often we would expect the two words to co-occur assuming they each occurred independently; recall that the probability of two independent events both occurring is just the product of the probabilities of the two events. Thus, the ratio gives us an estimate of how much more the two words co-occur than we expect by chance. PMI is a useful tool whenever we need to find words that are strongly associated.