As per usual with reflection problems instead of bouncing off the sides of a $1 \times 1$ square we imagine the ball to travel in a straight line from origin in an infinite grid of $1 \times 1$ squares, 'bouncing' every time it meets a line $x=m$ or $y=n$. Let the lattice point it first meets after leaving the origin be $(a, b)$, so that $b>a$. Note that $a$ and $b$ are coprime, otherwise the ball will reach a vertex before the 2012th bounce. We wish to minimize the slope of the line to this point from origin, which is $b / a$. Now, the number of bounces up to this point is $a-1+b-1=a+b-2$, so the given statement is just $a+b=2014$. To minimize $b / a$ with $a$ and $b$ relatively prime, we must have $a=1005, b=1009$, so that the angle is $\tan^{-1}\left(\frac{1009}{1005}\right)$