Dissociation branching ratios of electronically excited OD⁺ transients

We investigate electronically excited OD⁺ transients formed in sequential fragmentation of heavy water dications following double ionization by a single photon. The dissociation of these excited OD⁺ states, driven by spin-orbit coupling and charge transfer, leads to either D⁺ + O(³P) or D(²S) + O⁺(⁴S) final products. We show that the branching ratio of these dissociation channels is a direct measure of the key transition probabilities, specifically A³Π → X³Σ⁻ → B³Σ⁻, and measure it as a function of energy above the dissociation limit for two specific states of OD⁺.