State-specific dynamics of unimolecular dissociation

摘要: This chapter discusses the state-specific dynamics of unimolecular dissociation. Unimolecular dissociation is one simplest types irreversible chemical reactions. It takes place in a single isolated molecule with an internal energy that exceeds first threshold. The also concept discrete metastable states (resonances) continuum. Resonances help to treat spectroscopic and kinetic aspects on equal grounds—they are spectroscopically measurable and, at same time, which can be temporally trapped, so it stabilized collisions ‘bath’ particles. elaborates resonance formulation decay, principal this approach using simple one-dimensional models, points out possible generalizations multidimensional case. describes experimental approaches for measuring state-resolved rates, such as promotion excited electronic state along electronically nonadiabatic transition ground subsequent ground-state potential surface (PES), overtone pumping, stimulated emission pumping. practical computing spectra polyatomic molecules described.