An open-source framework for analyzing N-electron dynamics. I. Multideterminantal wave functions.

The aim of the present contribution is to provide a framework for analyzing and visualizing the correlated many-electron dynamics of molecular systems, where an explicitly time-dependent electronic wave packet is represented as a linear combination of N-electron wave functions. The central quantity of interest is the electronic flux density, which contains all information about the transient electronic density, the associated phase, and their temporal evolution. It is computed from the associated one-electron operator by reducing the multideterminantal, many-electron wave packet using the Slater-Condon rules. Here, we introduce a general tool for post-processing multideterminant configuration-interaction wave functions obtained at various levels of theory. It is tailored to extract directly the data from the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions. The procedure is implemented in the open-source Python program detCI@ORBKIT, which shares and builds on the modular design of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). The new procedure is applied to ultrafast charge migration processes in different molecular systems, demonstrating its broad applicability. Convergence of the N-electron dynamics with respect to the electronic structure theory level and basis set size is investigated. This provides an assessment of the robustness of qualitative and quantitative statements that can be made concerning dynamical features observed in charge migration simulations. © 2017 Wiley Periodicals, Inc.