We prove that the first gap of $\mathbb R$-complementary thresholds of surfaces is $\frac{1}{13}$. More precisely, the largest $\mathbb R$-complementary threshold for surfaces that is strictly less than $1$ is $\frac{12}{13}$. This result has many applications in explicit birational geometry of surfaces and threefolds and allows us to find several other optimal bounds on surfaces. We show that the first gap of global log canonical threshold for surfaces is $\frac{1}{13}$, answering a question of V. Alexeev and W. Liu. We show that the minimal volume of log surfaces with reduced boundary and ample log canonical divisor is $\frac{1}{462}$, answering a question of J. Koll\'ar. We show that the smallest minimal log discrepancy (mld) of exceptional surfaces is $\frac{1}{13}$. As a special case, we show that the smallest mld of klt Calabi-Yau surfaces is $\frac{1}{13}$, reproving a recent result of L. Esser, B. Totaro, and C. Wang. After a more detailed classification, we classify all exceptional del Pezzo surfaces that are not $\frac{1}{11}$-lt, and show that the smallest mld of exceptional del Pezzo surfaces is $\frac{3}{35}$. We also get better upper bounds of $n$-complements and Tian's $\alpha$-invariants for surfaces. Finally, as an analogue of our main theorem in high dimensions, we propose a question associating the gaps of $\mathbb R$-complementary thresholds with the gaps of mld's and study some special cases of this question.