$A =\{1,2,3\}$ and $B=\{a,b\}$
Based on the text, the number of relations between sets can be calculated using $2^{mn}$ where $m$ and $n$ represent the number of members in each set.
Given this, I calculated this number to be $2^{6}=64$ but this number seems too large.
Did I correctly calculate this value?
Yes, you did. There are $3 \cdot 2=6$ pairs of one element from $A$ and one from $B$. Each of these pairs can be in the relation or not, so you have six twofold choices that are independent. That gives $2^6=64$