A reduced-cost third-order algebraic diagrammatic construction based on state-specific frozen natural orbitals: Application to the electron-attachment problem

TL;DR

This paper introduces a computationally efficient third-order algebraic diagrammatic construction method for electron attachment problems, utilizing state-specific frozen natural orbitals to reduce cost and improve accuracy, especially for large basis sets.

Contribution

The authors develop a reduced-cost EA-ADC(3) method based on state-specific frozen natural orbitals, density fitting, and perturbative corrections, enhancing efficiency and accuracy over traditional approaches.

Findings

Significant speedup over conventional EA-ADC(3) methods.

Effective in calculating electron affinities with large basis sets.

Accurately describes non-valence correlation-bound anions.

Abstract

We have developed a reduced-cost non-Dyson third-order algebraic diagrammatic construction theory for the electron-attachment problem based on state-specific frozen natural orbitals. Density fitting and truncated natural auxiliary functions were employed to enhance computational efficiency. The use of state-specific frozen natural orbitals significantly decreases the virtual space and provides a notable speedup over the conventional EA-ADC(3) method with a systematically controllable accuracy. A perturbative correction for the truncated natural orbitals significantly reduces the error in the calculated electron affinity values. The method also shows sufficient accuracy in the case of non-valence correlation-bound anions, where the local approximation-based methods fail. The efficiency of the method is demonstrated by performing an EA-ADC(3) calculation with more than 1300 basis functions.