Electronic Non-adiabatic Dynamics in Enhanced Ionization of Isotopologues of H2+ from the Exact Factorization Perspective
Physical Chemistry Chemical Physics 19, 8269 - 8281 (2017)
Electronic Non-adiabatic Dynamics in Enhanced Ionization of Isotopologues of H2+ from the Exact Factorization Perspective
It was recently shown that the exact potential driving the electron's dynamics in enhanced ionization of H2+ can have large contributions arising from dynamical electron-nuclear correlation, going beyond what any electrostatics-based model can provide[1]. This potential is defined via the exact factorization of the molecular wavefunction that allows the construction of a Schroedinger equation for the electronic system, in which the potential contains exactly the effect of coupling to the nuclear system and any external fields. Here we study enhanced ionization in isotopologues of H+2 in order to investigate nuclear-mass-dependence of these terms for this process. We decompose the exact potential into components that naturally arise from the conditional wavefunction, and also into components arising from the marginal electronic wavefunction, and compare the performance of propagation on these different components as well as approximate potentials based on the quasi-static or Hartree approximation with the exact propagation. A quasiclassical analysis is presented to help analyse the structure of different non-electrostatic components to the potential driving the ionizing electron.
Additional Information
- Download
- Preprint - 5.32 MB
- Doi
- http://dx.doi.org/10.1039/c6cp08539c
- arxiv
- http://arxiv.org/abs/ arXiv:1612.00507
- Notes
- We acknowledge support from the European Research Council (ERC-2015-AdG-694097), Grupos Consolidados (IT578-13), and the European Union’s Horizon 2020 Research and Innovation programme under grant agreement no. 676580. A. K. and A. A. acknowledge funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska- Curie grant agreement no. 704218 and 702406, respectively. N. T. M. thanks the National Science Foundation, grant CHE-1566197, for support. Open Access funding provided by the Max Planck Society.