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

Fuente: arXiv
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Main Authors: Mukhopadhyay, Tamoghna, Majee, Kamal, Dutta, Achintya Kumar
Format: Preprint
Published: 2025
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author Mukhopadhyay, Tamoghna
Majee, Kamal
Dutta, Achintya Kumar
author_facet Mukhopadhyay, Tamoghna
Majee, Kamal
Dutta, Achintya Kumar
contents 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.
format Preprint
id arxiv_https___arxiv_org_abs_2511_05897
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle A reduced-cost third-order algebraic diagrammatic construction based on state-specific frozen natural orbitals: Application to the electron-attachment problem
Mukhopadhyay, Tamoghna
Majee, Kamal
Dutta, Achintya Kumar
Chemical Physics
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.
title A reduced-cost third-order algebraic diagrammatic construction based on state-specific frozen natural orbitals: Application to the electron-attachment problem
topic Chemical Physics
url https://arxiv.org/abs/2511.05897