[step:Classify the simply-laced positive definite trees]
Assume first that every edge of $\Delta$ is a single edge. Then $S=2I-M$, where $M$ is the adjacency matrix of the tree $\Gamma$.
[claim:There is at most one branching vertex, and every branching vertex has degree three]
[/claim]
[proof]
For a finite path with $p\geq 1$ vertices, let $T_p$ denote the $p\times p$ symmetric matrix with diagonal entries $2$ and off-diagonal entries $-1$ between adjacent vertices. Its leading determinants $d_p:=\det T_p$ satisfy
\begin{align*}
d_0&:=1,\qquad d_1:=2,\qquad d_p=2d_{p-1}-d_{p-2}\quad (p\geq 2),
\end{align*}
so $d_p=p+1$. [Cramer's rule](/theorems/3305) applied to the first diagonal entry gives
\begin{align*}
(T_p^{-1})_{11}=\frac{d_{p-1}}{d_p}=\frac{p}{p+1}.
\end{align*}
Let $v$ be a vertex of degree $d\geq 3$. Choose the full subdiagram consisting of $v$ and the $d$ branches issuing from $v$, with branch lengths $p_1,\dots,p_d\in\mathbb{N}$. Ordering the vertices with $v$ first, its symmetric matrix has block form
\begin{align*}
S_v=
\begin{pmatrix}
2&-e_1^\top&-e_1^\top&\cdots&-e_1^\top\\
-e_1&T_{p_1}&0&\cdots&0\\
-e_1&0&T_{p_2}&\cdots&0\\
\vdots&\vdots&\vdots&\ddots&\vdots\\
-e_1&0&0&\cdots&T_{p_d}
\end{pmatrix},
\end{align*}
where $e_1\in\mathbb{R}^{p_\ell}$ denotes the first standard basis vector in the corresponding branch block. Since each $T_{p_\ell}$ is positive definite, the Schur complement criterion gives that $S_v$ is positive definite exactly when
\begin{align*}
2-\sum_{\ell=1}^{d} e_1^\top T_{p_\ell}^{-1}e_1
&=2-\sum_{\ell=1}^{d}\frac{p_\ell}{p_\ell+1}\\
&=2-d+\sum_{\ell=1}^{d}\frac{1}{p_\ell+1}
>0.
\end{align*}
Thus positivity of this principal submatrix requires
\begin{align*}
\sum_{\ell=1}^{d}\frac{1}{p_\ell+1}>d-2.
\end{align*}
Since $p_\ell\geq 1$ for each $\ell$, the left-hand side is at most $d/2$. If $d\geq 4$, then $d/2\leq d-2$, with equality only when $d=4$ and all $p_\ell=1$. The strict inequality is therefore impossible. Hence every branching vertex has degree three.
It remains to exclude two branching vertices. Suppose that $u$ and $v$ are distinct degree-three vertices, and let the path from $u$ to $v$ contain $t\geq 1$ edges. Choose two terminal branches at $u$ not containing $v$ and two terminal branches at $v$ not containing $u$; let their lengths be $p_1,p_2,q_1,q_2\in\mathbb{N}$. The full subdiagram on these four branches and the path from $u$ to $v$ is a tree with two degree-three vertices. Define $x\in\mathbb{R}^{I}$ as follows: put $x_u=x_v=1$, put value $1$ on every internal vertex of the path from $u$ to $v$, and on a terminal branch of length $p$ attached to either branching vertex put the values
\begin{align*}
1-\frac{1}{p+1},\ 1-\frac{2}{p+1},\ \dots,\ 1-\frac{p}{p+1}
\end{align*}
away from the branching vertex. Put $x_i=0$ outside this full subdiagram. Using
\begin{align*}
Q(x)=\sum_{\{i,j\}\text{ edge}}(x_i-x_j)^2+\sum_{i\in I}(2-\deg i)x_i^2
\end{align*}
for simply-laced trees, the path from $u$ to $v$ contributes $0$ to the edge-square sum, each of the four terminal branches contributes $1/(p+1)$ or $1/(q+1)$ after its endpoint term is included, and the two degree-three vertices contribute $-1$ each through $(2-\deg i)x_i^2$. Hence
\begin{align*}
Q(x)=\frac{1}{p_1+1}+\frac{1}{p_2+1}+\frac{1}{q_1+1}+\frac{1}{q_2+1}-2\leq 0,
\end{align*}
because each of the four fractions is at most $1/2$. This contradicts positive definiteness of the principal submatrix on the chosen full subdiagram. Therefore there is at most one branching vertex.
[/proof]
If there is no branching vertex, the tree is a path, hence the diagram is $A_n$ for some $n\geq 1$.
If there is a branching vertex, it has degree three. Let $p,q,r\in\mathbb{N}$ be the three branch lengths, ordered so that
\begin{align*}
1\leq p\leq q\leq r.
\end{align*}
The Schur complement computation in the claim, now with $d=3$, proves that the symmetric matrix is positive definite exactly when
\begin{align*}
\frac{1}{p+1}+\frac{1}{q+1}+\frac{1}{r+1}>1.
\end{align*}
Indeed, the branch matrices $T_p,T_q,T_r$ are positive definite, and the remaining Schur complement is precisely this displayed quantity. If $p=1$ and $q=1$, this inequality holds for every $r\geq 1$, producing the diagrams $D_n$ with $n=r+3\geq 4$. If $p=1$ and $q=2$, then
\begin{align*}
\frac12+\frac13+\frac{1}{r+1}>1,
\end{align*}
so $r+1<6$, and hence $r=2,3,4$, producing $E_6,E_7,E_8$. If $q\geq 3$, then
\begin{align*}
\frac{1}{p+1}+\frac{1}{q+1}+\frac{1}{r+1}\leq \frac12+\frac14+\frac14=1,
\end{align*}
which violates strict positivity. Thus the simply-laced finite-type connected diagrams are exactly
\begin{align*}
A_n,\quad D_n,\quad E_6,\quad E_7,\quad E_8.
\end{align*}
[/step]