Autoionizing electronic states are ubiquitous in highly energetic environment; they also play an important role in the photophysics of anions (including biochromophores) and in the condensed-phase processes, e.g. DNA damage by secondary electrons. Accurate prediction of the lifetimes of autoionizing states is crucial for understanding the dynamics and chemical properties of these systems. We present a new set of methods exploiting complex scaling (CS) formalism [1] to extend the capabilities of conventional equation-of-motion coupled-cluster (EOM-CCSD) approaches [2] to description of resonance states energies and lifetimes. Complex-scaling formalism allows one to isolate a solution corresponding to a resonance state as a single eigenfunction of the scaled Hamiltonian with a complex eigenvalue. We demonstrate that the developed complex-scaled EOM-(EA/EE)-CCSD methods enable accurate prediction of both resonance positions and lifetimes in atoms. We discuss the role of electron correlation in the description of shape and Feshbach resonances. We also formulate the criteria for an optimal one-electron basis set choice for calculation of atomic resonances positions and lifetimes.[1] N. Moiseyev Physics Reports 1998, 302, 211-293.[2] A.I. Krylov  Ann. Rev. Phys. Chem. 2008, 59, 433-462.

Complex-scaled equation-of-motion coupled-cluster suite of methods for autoionizing states

246th National Meeting (2013)

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