Restricted Correlation Space B-Spline ADC Approach to Molecular Ionization: Theory and Applications to Total Photoionization Cross-Sections.

Abstract

Herein is presented a new approach to the ab initio algebraic diagrammatic construction (ADC) schemes for the polarization propagator, which is explicitly designed to accurately and efficiently describe molecular ionization. The restricted correlation space (RCS) version of the ADC methods up to second order of perturbation theory is derived via the intermediate state representation (ISR) and implemented in the multicenter B-spline basis set for the electronic continuum. Remarkably a general close-coupling structure of the RCS-ADC many-electron wave function, connecting the N-particle to the ( N - 1)-particle ADC intermediate states, emerges naturally as a nontrivial result of the RCS ansatz. Moreover, the introduced RCS-ADC schemes prove to be particularly manageable from a computational point of view, overcoming the practical limitations of the conventional ADC approaches. The quality of the new RCS-ADC( n) approaches is verified by performing a series of total photoionization cross-section calculations on a test set of molecules. The excellent agreement of the results with existing accurate benchmarks demonstrates that the RCS versions of the ADC schemes are optimal and quantitatively accurate methods for studying multichannel molecular photoionization.