Let $a=a_{i\in n}$ is an ordinal-indexed family of ordinals.
I call a structured sum of $a$ an order isomorphism from the lexicographically ordered set $\{ \left( i ; x \right) \; | \; i \in n, x\in a_i \}$ into $\sum a$.
I suspect that for every $a$ there exist exactly one structured sum. Right? I am also attempting to write an explicit formula for structured sum having specified $a$.
Can you point me any reference where the thing which I call structured sums are studied? I wouldn't be happy to know that I am the person which first discovered structured sums :-)
Let $$X=\bigcup_{i\in n}\Big(\{i\}\times a_i\Big)\;,$$ and let $\prec$ denote the lexicographic order on $X$. Then you’re simply looking at the order isomorphism $$\varphi:X\to\sum_{i\in n}a_i\;,$$ where the sum on the right is ordinal addition. Let $\alpha$ be this ordinal sum, and for $\langle i,\xi\rangle\in X$ let $$X(i,\xi)=\{\langle j,\zeta\rangle\in X:\langle j,\zeta\rangle\prec\langle i,\xi\rangle\}\;,$$ the set of all $\prec$-predecessors of $\langle i,\xi\rangle$ in $X$. Then clearly
$$\varphi\left(\langle i,\xi\rangle\right)=\inf\left(\alpha\setminus\varphi\left[X(i,\xi)\right]\right)\;.$$
I doubt that in general you can say much more than this and a few straightforward observations like $$\varphi\left(\langle i,\xi\rangle\right)=\varphi\left(\langle i,0\rangle\right)+\xi=\alpha_i+\xi\;,$$ where we define $\alpha_i=\sum_{j<i}a_j$.