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Published on: May 27, 2020
A reduced-cost third-order algebraic diagrammatic construction method based on state-specific frozen natural
Tamoghna Mukhopadhyay1, Kamal Majee1, Achintya Kumar Dutta1,2
1Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
None:
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 reduces the size of the virtual space and provides a notable speedup over the conventional EA-ADC(3) method with 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.
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