Many-Body Basis Set Amelioration Method for Incremental Full Configuration Interaction

Fuente: arXiv
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Autori principali: Hatch, Jeffrey P, Rask, Alan E, Dang, Duy-Khoi, Zimmerman, Paul M
Natura: Preprint
Pubblicazione: 2024
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author Hatch, Jeffrey P
Rask, Alan E
Dang, Duy-Khoi
Zimmerman, Paul M
author_facet Hatch, Jeffrey P
Rask, Alan E
Dang, Duy-Khoi
Zimmerman, Paul M
contents Incremental full configuration interaction (iFCI) is polynomial-cost approach to the FCI limit of electronic structure. This article introduces the many-body basis set amelioration (MBBSA) method, which is designed to allow iFCI to be applicable to larger atomic orbital basis sets. MBBSA uses a series of inexpensive iFCI calculations to approximate the correlation energy that would be found using a more expensive, highly accurate iFCI calculation. When compared to standard iFCI computations on smaller molecules in triple-zeta and larger basis sets, MBBSA provides approximations to total and relative energies within chemical accuracy. MBBSA yields cost savings of between 60 and 92% when compared to standard iFCI calculations, with larger systems having increased savings. Tests of MBBSA on two reactions that involve highly correlated systems, the automerization of cyclobutadiene and a Criegee intermediate reaction, show that MBBSA has practical utility for studying realistic chemistries.
format Preprint
id arxiv_https___arxiv_org_abs_2410_13001
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Many-Body Basis Set Amelioration Method for Incremental Full Configuration Interaction
Hatch, Jeffrey P
Rask, Alan E
Dang, Duy-Khoi
Zimmerman, Paul M
Chemical Physics
Incremental full configuration interaction (iFCI) is polynomial-cost approach to the FCI limit of electronic structure. This article introduces the many-body basis set amelioration (MBBSA) method, which is designed to allow iFCI to be applicable to larger atomic orbital basis sets. MBBSA uses a series of inexpensive iFCI calculations to approximate the correlation energy that would be found using a more expensive, highly accurate iFCI calculation. When compared to standard iFCI computations on smaller molecules in triple-zeta and larger basis sets, MBBSA provides approximations to total and relative energies within chemical accuracy. MBBSA yields cost savings of between 60 and 92% when compared to standard iFCI calculations, with larger systems having increased savings. Tests of MBBSA on two reactions that involve highly correlated systems, the automerization of cyclobutadiene and a Criegee intermediate reaction, show that MBBSA has practical utility for studying realistic chemistries.
title Many-Body Basis Set Amelioration Method for Incremental Full Configuration Interaction
topic Chemical Physics
url https://arxiv.org/abs/2410.13001