Lawrence Berkeley National Laboratory
Hybrid-Basis Close-Coupling Interface to Quantum Chemistry Packages for the Treatment of Ionization Problems.
- Author(s): Marante, Carlos
- Klinker, Markus
- Corral, Inés
- González-Vázquez, Jesús
- Argenti, Luca
- Martín, Fernando
- et al.
Published Web Locationhttps://pubs.acs.org/doi/10.1021/acs.jctc.6b00907
The theoretical description of observables in attosecond pump-probe experiments requires a good representation of the system's ionization continuum. For polyelectronic molecules, however, this is still a challenge, due to the complicated short-range structure of correlated electronic wave functions. Whereas quantum chemistry packages (QCP) implementing sophisticated methods to compute bound electronic molecular states are well-established, comparable tools for the continuum are not widely available yet. To tackle this problem, we have developed a new approach that, by means of a hybrid Gaussian-B-spline basis, interfaces existing QCPs with close-coupling scattering methods. To illustrate the viability of this approach, we report results for the multichannel ionization of the helium atom and of the hydrogen molecule that are in excellent agreement with existing accurate benchmarks. These findings, together with the versatility of QCPs to describe a broad range of chemical systems, indicate that this is a valid approach to study the ionization of polyelectronic systems in which correlation and exchange symmetry play a major role.