From numerical experiments, it seems that the optimum is to have one die only show $1$ or $6$ with probability $\frac12$ each, and to use probabilities $\left(\frac18,\frac3{16},\frac3{16},\frac3{16},\frac3{16},\frac18\right)$ for the other die. The probabilities for the sums are then $\frac1{16}$ for $2$ and $12$, $\frac18$ for $7$ and $\frac3{32}$ for all other values. I can show that this is a local optimum, but I don't know how to show that it's a global optimum. The probability to get the same sum twice using these probabilities is $\frac3{32}=0.09375$, pretty close to the lower bound $\frac1{11}=0.\overline{09}$ that would be achieved if all sums had the same probability. This is to be compared to $\frac{73}{648}\approx0.11265$ for fair dice, so the distance to the lower bound has been reduced to $13\%$ of its value for fair dice. Interestingly, if we allow negative probabilities, the optimum seems to be $\frac{11}{120}=0.91\overline6$, which just so happens to be a number I recently came across at Project Euler.
Also interestingly, the optimal symmetric solution isn't nearly as good. In a fully symmetric solution, both dice would have the same distribution, and the distribution would be invariant under the inversion $x\to7-x$. That plus normalisation leaves only two degrees of freedom, $p_1$ and $p_2$, with $p_3=\frac12-p_1-p_2$ determined by normalisation and the others by symmetry. Then the probability to get the same sum twice is
$$
2p_1^4+2(2p_1p_2)^2+2(2p_1p_3+p_2^2)^2+2(2p_1p_3+2p_2p_3)^2+2(2p_1p_2+2p_2p_3+p_3^2)^2+(2p_1^2+2p_2^2+2p_3^2)^2\\
=36 p_1^4+88 p_1^3 p_2-36 p_1^3+108 p_1^2 p_2^2-72 p_1^2 p_2+15 p_1^2+48 p_1 p_2^3-48 p_1 p_2^2+18 p_1 p_2-3 p_1+28 p_2^4-24 p_2^3+9 p_2^2-2 p_2+\frac38
$$
(Wolfram|Alpha calculation), and minimizing this yields
$$
p_1\approx0.243883\;,\\
p_2\approx0.137479\;,\\
p_3\approx0.118638\;,\\
$$
with probability $\approx0.104303$ of getting the same sum (Wolfram|Alpha calculation), which reduces the difference from the lower bound only to about $62\%$.
P.S.: I did the same numerical investigations for three dice, and it seems that these are optimized if two of them show only $1$ or $6$ with probability $\frac12$ each and the third has probabilities $\left(\frac3{26},\frac5{26},\frac5{26},\frac5{26},\frac5{26},\frac3{26}\right)$. In this case the probability for coinciding sums is $\frac{15}{208}\approx0.07212$, compared to the lower bound $\frac1{16}=0.0625$. The probabilities for the sums in this case are $\frac1{104}(3,5,5,5,5,9,10,10,10,10,9,5,5,5,5,3)$.