Step 1: Use the given equation.
We are given that \( |\mathbf{a} - \mathbf{b}| = \frac{\sqrt{3}}{2} \). Using the formula for the magnitude of the difference of two vectors:
\[
|\mathbf{a} - \mathbf{b}| = \sqrt{|\mathbf{a}|^2 + |\mathbf{b}|^2 - 2 \mathbf{a} \cdot \mathbf{b}}
\]
Since \( \mathbf{a} \) and \( \mathbf{b} \) are unit vectors, \( |\mathbf{a}| = |\mathbf{b}| = 1 \), so the equation simplifies to:
\[
|\mathbf{a} - \mathbf{b}| = \sqrt{2 - 2 \mathbf{a} \cdot \mathbf{b}}
\]
Step 2: Substitute the given magnitude.
Substitute \( |\mathbf{a} - \mathbf{b}| = \frac{\sqrt{3}}{2} \) into the equation:
\[
\frac{\sqrt{3}}{2} = \sqrt{2 - 2 \mathbf{a} \cdot \mathbf{b}}
\]
Square both sides:
\[
\frac{3}{4} = 2 - 2 \mathbf{a} \cdot \mathbf{b}
\]
Step 3: Solve for \( \mathbf{a} \cdot \mathbf{b} \).
Rearrange the equation:
\[
2 \mathbf{a} \cdot \mathbf{b} = 2 - \frac{3}{4} = \frac{5}{4}
\]
So:
\[
\mathbf{a} \cdot \mathbf{b} = \frac{5}{8}
\]
Step 4: Find the angle between \( \mathbf{a} \) and \( \mathbf{b} \).
The dot product of two vectors is given by:
\[
\mathbf{a} \cdot \mathbf{b} = \cos \theta
\]
Thus:
\[
\cos \theta = \frac{5}{8}
\]
Therefore, the angle \( \theta \) is:
\[
\theta = \cos^{-1} \left( \frac{5}{8} \right)
\]
Thus, the angle between \( \mathbf{a} \) and \( \mathbf{b} \) is:
\[
\boxed{\cos^{-1} \left( \frac{5}{8} \right)}
\]