Quantum interference among competing unimolecular decay channels: Asymmetric S D2CO decay profiles

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Abstract
The dynamics of a state undergoing decay to a manifold of states coupled to a dissociative continuum is investigated in the weak coupling limit. The decay rate is found to be composed of terms symmetric and asymmetric in the relative energy difference between the initial state and the states in the manifold. The well‐known symmetric terms arise from resonantly enhanced decay of the initial state through each state in the manifold to the continuum. The newly identified asymmetric terms arise from interfering couplings of the initial state to the continuum through different states in the manifold, i.e., from off‐diagonal elements of the width matrix Γkk’ of the effective Hamiltonian describing dissociation of the states in the manifold. The general line shape derived here is used to fit asymmetric features in Stark level‐crossing spectra of D2CO. Statistical properties of the width matrix are summarized, and the relation between diagonal and off‐diagonal matrix element magnitudes is derived.

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