Metastable anions are ubiquitous in chemistry and biology. The information on the lifetime is crucial for understanding the processes involving the temporary anions states. Moreover, the lifetimes that are usually on the time-scale of the nuclear dynamics (fs-ps) lead to complex interplay between electronic decay and nuclear relaxation. Therefore, theoretical prediction of resonances position and width is of primary importance. We will describe recently developed theory for description of resonance electronic states, which is based on complex absorbing potential approach1 combined with extended multiconfigurational quasidegenerate perturbation theory method (XMCQDPT2)2. The method is capable of description of resonance ground and excited electronic states dominated by open shell configurations and by configurations of multiply excited character with respect to the closed shell reference. The performance is demonstrated for a test set of small molecules, as well as for biologically relevant species, e.g. quinones. [1] U. V. Riss and H.-D. Meyer, “Calculation of resonance energies and widths using the complex absorbing potential method,” J. Phys. B: At. Mol. Opt. Phys., vol. 26, p. 4503 (1993). [2] A. A. Granovsky, “Extended multi-configuration quasi-degenerate perturbation theory: The new approach to multi-state multi-reference perturbation theory,” J. Chem. Phys., vol. 134, p. 214113 (2011).

Complex absorbing potential extended multiconfigurational quasidegenerate perturbation theory

251st National Meeting (2016)

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