There are $6^5$ possible outcomes when five six-sided dice are rolled.
The number of outcomes in which the outcomes sum to $14$ is equal to the number of solutions of the equation
$$x_1 + x_2 + x_3 + x_4 + x_5 = 14 \tag{1}$$
in the positive integers subject to the constraints that $x_k \leq 6$ for $1 \leq k \leq 5$. The number of solutions of the equation
$$x_1 + x_2 + x_3 + \cdots + x_k = n$$
in the positive integers is given by the formula
$$\binom{n - 1}{k - 1}$$
Hence, equation 1 has
$$\binom{14 - 1}{5 - 1} = \binom{13}{4}$$
solutions.
From these, we must exclude those solutions in which one or more of the variables exceeds $6$. Note that at most one variable may exceed $6$ since $2 \cdot 7 + 3 \cdot 1 = 17 > 14$.
Suppose $x_1 \geq 7$. Let $x_1' = x_1 - 6$. Then $x_1'$ is a positive integer. Substituting $x_1' + 6$ for $x_1$ in equation 1 yields
\begin{align*}
x_1' + 6 + x_2 + x_3 + x_4 + x_5 & = 14\\
x_1' + x_2 + x_3 + x_4 + x_5 + x_6 & = 8 \tag{2}
\end{align*}
Equation 2 is an equation in the positive integers with
$$\binom{8 - 1}{5 - 1} = \binom{7}{4}$$
solutions.
By symmetry, there are an equal number of solutions for each variable that could exceed $6$. Hence, the number of solutions of equation 1 in which one of the five variables exceeds $6$ is
$$\binom{5}{1}\binom{7}{4}$$
Hence, the number of solutions of equation 1 that satisfy the constraints is
$$\binom{13}{4} - \binom{5}{1}\binom{7}{4} = 715 - 5 \cdot 35 = 540$$
Therefore, the desired probability is
$$\frac{\binom{13}{4} - \binom{5}{1}\binom{7}{4}}{6^5} = \frac{540}{7776} = \frac{5}{72}$$