The density matrix via few dominant observables: The quantum interference in the isotope effect for atto-pumped N2.

Abstract

Atto- and sub-femto-photochemistry enables preparation of molecules in a coherent superposition of several electronic states. Recently [Ajay et al., Proc. Natl. Acad. Sci. U. S. A. 115, 5890-5895 (2018)], we examined an effect of the nuclear mass during the non-adiabatic transfer between strongly coupled Rydberg and valence electronic states in N2 excited by an ultrafast pulse. Here, we develop and analyze an algebraic description for the density matrix and its logarithm, the surprisal, in such a superposition of states with a focus on the essentially quantum effect of mass. This allows for the identification of a few observables that accurately characterize the density matrix of the system with several coupled electron-nuclear states. We compact the time evolution in terms of time-dependent coefficients of these observables. Using the few observables, we derive an analytical expression for the time-dependent surprisal. This provides a mass-dependent phase factor only in the observables off-diagonal in the electronic index. The isotope effect is shown to be explicitly driven by the shift in the equilibrium position of the valence state potential. It is analytically given as a time-dependent phase factor describing the interference in the overlap of the two wave packets on the coupled electronic states. This phase factorizes as a product of classical and quantal contributions.