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Tensor-Hypercontracted MP2 First Derivatives: Runtime and Memory Efficient Computation of Hyperfine Coupling Constants
[Image: see text] We employ our recently introduced tensor-hypercontracted (THC) second-order Møller–Plesset perturbation theory (MP2) method [Bangerter, F. H., Glasbrenner, M., Ochsenfeld, C. J. Chem. Theory Comput.2021, 17, 211–221] for the computation of hyperfine coupling constants (HFCCs). The...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9476664/ https://www.ncbi.nlm.nih.gov/pubmed/35943450 http://dx.doi.org/10.1021/acs.jctc.2c00118 |
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author | Bangerter, Felix H. Glasbrenner, Michael Ochsenfeld, Christian |
author_facet | Bangerter, Felix H. Glasbrenner, Michael Ochsenfeld, Christian |
author_sort | Bangerter, Felix H. |
collection | PubMed |
description | [Image: see text] We employ our recently introduced tensor-hypercontracted (THC) second-order Møller–Plesset perturbation theory (MP2) method [Bangerter, F. H., Glasbrenner, M., Ochsenfeld, C. J. Chem. Theory Comput.2021, 17, 211–221] for the computation of hyperfine coupling constants (HFCCs). The implementation leverages the tensor structure of the THC factorized electron repulsion integrals for an efficient formation of the integral-based intermediates. The computational complexity of the most expensive and formally quintic scaling exchange-like contribution is reduced to effectively subquadratic, by making use of the intrinsic, exponentially decaying coupling between tensor indices through screening based on natural blocking. Overall, this yields an effective subquadratic scaling with a low prefactor for the presented THC-based AO-MP2 method for the computation of isotropic HFCCs on DNA fragments with up to 500 atoms and 5000 basis functions. Furthermore, the implementation achieves considerable speedups with up to a factor of roughly 600–1000 compared to previous implementations [Vogler, S., Ludwig, M., Maurer, M., Ochsenfeld, C. J. Chem. Phys.2017, 147, 024101] for medium-sized organic radicals, while also significantly reducing storage requirements. |
format | Online Article Text |
id | pubmed-9476664 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-94766642022-09-16 Tensor-Hypercontracted MP2 First Derivatives: Runtime and Memory Efficient Computation of Hyperfine Coupling Constants Bangerter, Felix H. Glasbrenner, Michael Ochsenfeld, Christian J Chem Theory Comput [Image: see text] We employ our recently introduced tensor-hypercontracted (THC) second-order Møller–Plesset perturbation theory (MP2) method [Bangerter, F. H., Glasbrenner, M., Ochsenfeld, C. J. Chem. Theory Comput.2021, 17, 211–221] for the computation of hyperfine coupling constants (HFCCs). The implementation leverages the tensor structure of the THC factorized electron repulsion integrals for an efficient formation of the integral-based intermediates. The computational complexity of the most expensive and formally quintic scaling exchange-like contribution is reduced to effectively subquadratic, by making use of the intrinsic, exponentially decaying coupling between tensor indices through screening based on natural blocking. Overall, this yields an effective subquadratic scaling with a low prefactor for the presented THC-based AO-MP2 method for the computation of isotropic HFCCs on DNA fragments with up to 500 atoms and 5000 basis functions. Furthermore, the implementation achieves considerable speedups with up to a factor of roughly 600–1000 compared to previous implementations [Vogler, S., Ludwig, M., Maurer, M., Ochsenfeld, C. J. Chem. Phys.2017, 147, 024101] for medium-sized organic radicals, while also significantly reducing storage requirements. American Chemical Society 2022-08-09 2022-09-13 /pmc/articles/PMC9476664/ /pubmed/35943450 http://dx.doi.org/10.1021/acs.jctc.2c00118 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Bangerter, Felix H. Glasbrenner, Michael Ochsenfeld, Christian Tensor-Hypercontracted MP2 First Derivatives: Runtime and Memory Efficient Computation of Hyperfine Coupling Constants |
title | Tensor-Hypercontracted
MP2 First Derivatives: Runtime
and Memory Efficient Computation of Hyperfine Coupling Constants |
title_full | Tensor-Hypercontracted
MP2 First Derivatives: Runtime
and Memory Efficient Computation of Hyperfine Coupling Constants |
title_fullStr | Tensor-Hypercontracted
MP2 First Derivatives: Runtime
and Memory Efficient Computation of Hyperfine Coupling Constants |
title_full_unstemmed | Tensor-Hypercontracted
MP2 First Derivatives: Runtime
and Memory Efficient Computation of Hyperfine Coupling Constants |
title_short | Tensor-Hypercontracted
MP2 First Derivatives: Runtime
and Memory Efficient Computation of Hyperfine Coupling Constants |
title_sort | tensor-hypercontracted
mp2 first derivatives: runtime
and memory efficient computation of hyperfine coupling constants |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9476664/ https://www.ncbi.nlm.nih.gov/pubmed/35943450 http://dx.doi.org/10.1021/acs.jctc.2c00118 |
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