We say that a $k$-ary relation $r$ over $\mathbb{N}$ is arithmetical if there is a formula $\varphi (\vec{a})$ with $k$ free variables $\vec{a}$, such that, for every $\vec{n}=(n_1,\dots, n_k)\in\mathbb{N}^k$,
$$r(\vec{n}) \text{ holds }\ \text{ iff }\ \ \mathbf{N}\vDash\varphi(\vec{\underline{n}})$$
Where $\mathbf{N}$ is the standard model of arithmetic (that is, $\mathbf{N}=\langle\mathbb{N}, +, \cdot, s, 0, =\rangle$), $\vec{\underline{n}}$ is the $k$-tuple $(\underline{n_1},\dots,\underline{n_k})$ and $\underline{n_i}$ is the $n_i$ application of the $s$ symbol to the $0$ symbol (that is, $ss\cdots ss0$ $\ n_i$ times).
We say that a function is arithmetical iff it is arithmetical as a relation.
It is possible to prove that any recursively enumerable set $R$ is arithmetical. However, I don't find the converse anywhere, yet, I don't know how to obtain an arithmetical set which is not a recursively enumerable one.
My first question is if all arithmetical sets are recursively enumerable or if there is a counterexample of this.
And, if there is a counterexample, I have another question.
In case of total functions, we have that a total function $f$ is recursive iff there is a formula $\varphi(\vec{a},b)$ with $k+1$ free variables $\vec{a}, b$ such that
$f(\vec{n})=m$ implies $\text{PA}\vdash \varphi(\underline{\vec{n}}, \underline{m})$ for all $\vec{n}, m\in\mathbb{N}$
$\text{PA}\vdash\exists b (\varphi(\underline{\vec{n}}, b)\wedge (\forall c (\varphi(\underline{\vec{n}}, c)\rightarrow b=c)))$ (where $\text{PA}$ is the Peano Arithmetic theory).
This definition looks to me as an stronger version of the first one. In particular, since we know that there is arithmetical sets which are not recursive (since not any recursively enumerable set is recursive) we have a similar characterization for total formulas which are defined, instead of $\mathbf{N}$, in Peano Arithmetic (so in fact we have a characterization for recursive sets in terms of definability in $\text{PA}$ since its characteristic function is a total recursive function with ones and zeroes as possible outputs).
My second question is, if there is some arithmetical set which is not a recursively enumerable set, is there any characterization in terms of definability between this other two?
Summarizing, is there any arithmetical set which is not a recursively enumerable set? and if the answer is yes, is there any characterization in terms of definability with natural numbers for recursively enumerable sets?
Thanks