According to @Hippalectryon 's argument the probability that the first half pill is picked on day $n$ amounts to $$P(n)={n-1\over 100^{\>n}}\prod_{k=1}^{n-1}(101-k)\ .$$ It follows that $$f(n):={P(n+1)\over P(n)}={n(101-n)\over 100(n-1)}\ .$$ One easily checks that $f$ is monotonically decreasing in the relevant domain. Furthermore $$f(10)={91\over 90}>1,\qquad f(11)={99\over100}<1\ .$$ This shows that the $P(n)$ are increasing from $n=1$ up to $n=11$, and then are decreasing forever. The maximal occurring $p(n)$ is therefore $$P(11)\doteq0.0628157\ .$$