States lie in Hilbert space $\mathcal{H_S}$.
- $|\psi\rangle \in \mathcal{H_S}\,.$
- If you have $n$ qubits, then $\text{dim}(\mathcal{H_S}) = 2^n = d\,.$
Operators, density operators lie in the bounded operator space of $\mathcal{H}_S$.
- $\rho \in \mathcal{B}(\mathcal{H}_S)\,. $
- $\text{dim}(\mathcal{B}(\mathcal{H}_S)) = d \times d = d^2\,.$
Kraus operators are operators acting on $\mathcal{H_S}$. You have $d^2$ degrees of freedom, which requires $d^2$ basis to describe it.
If your map $\mathcal{E}$ is
$$ \mathcal{E}(\rho) = \sum_{n} K_{n} \rho K_{n}^{\dagger}\,, $$
Then you can write your Kraus operators in $\{\Gamma_{\alpha}\}$ basis as
$$ K_{n} = \sum_{\alpha=0}^{d^2-1} b_{n\alpha} \Gamma_{\alpha}\,, $$
where $b_{n\alpha}$ are the coefficients for the linear combination using the new basis; therefore, you will have total $d^2$ terms in the summation. $K_n$ is a $d \times d $ matrix.
Now, rewriting our map in terms of Kraus operators in the $\{\Gamma_{\alpha}\}$ basis gives us
$$
\begin{align}
\mathcal{E}(\rho) &= \sum_{n} K_{n} \rho K_{n}^{\dagger}\\
&= \sum_n \bigg(\sum_{\alpha=0}^{d^2-1} b_{n\alpha} \Gamma_{\alpha} \bigg) \rho \bigg(\sum_{\beta=0}^{d^2-1} b_{n\beta}^* \Gamma_{\beta}^{\dagger}\bigg)\\
&= \sum_{\alpha=0,\beta=0}^{d^2-1, d^2-1} \big(\sum_n b_{n\alpha} \cdot b_{n\beta}^* \big) \Gamma_{\alpha} \rho \Gamma_{\beta}^{\dagger}\\
&= \sum_{\alpha=0,\beta=0}^{d^2-1, d^2-1} \chi_{\alpha \beta}\Gamma_{\alpha} \rho \Gamma_{\beta}^{\dagger} \\
\end{align}
$$
So, as you can see above, Kraus operators being $d \times d$ results in $\chi$ having $d^2 \times d^2$ degrees of freedom. The process matrix is just
$$ \chi = bb^{\dagger} $$
where $b$ is the matrix with linear combination coefficients for your Kraus operators in $\{\Gamma_{\alpha}\}$ basis.