The probability of obtaining a sum of 4 on a single roll of two six-faced dice is calculated by considering all possible outcomes that result in a sum of 4. These outcomes are:
\[
(1, 3), (2, 2), (3, 1)
\]
So, there are 3 favorable outcomes for a sum of 4. Since there are 36 total outcomes when rolling two dice, the probability of getting a sum of 4 in one roll is:
\[
P(\text{sum of 4}) = \frac{3}{36} = \frac{1}{12} \approx 0.0833
\]
We are asked to find the probability that the sum of 4 occurs in exactly two of the three rolls. This is a binomial probability problem, where we want exactly two successes (sum of 4) in three trials (rolls). The binomial probability is given by:
\[
P(X = 2) = \binom{3}{2} \left( \frac{1}{12} \right)^2 \left( 1 - \frac{1}{12} \right)^{3 - 2}
\]
\[
P(X = 2) = 3 \times \left( \frac{1}{12} \right)^2 \times \left( \frac{11}{12} \right)
\]
\[
P(X = 2) \approx 3 \times \frac{1}{144} \times \frac{11}{12} \approx 0.0206
\]
Thus, the probability that the sum of 4 occurs in exactly two of the three rolls is:
\[
\boxed{0.021}
\]