Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness
Recent algorithmic and hardware advances have enabled the application of electronic structure methods to the study of large-scale systems such as proteins with O(103) atoms. Most such methods benefit greatly from the use of reduced basis sets to further enhance their speed, but truly minimal basis s...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society
2017
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| Online Access: | http://hdl.handle.net/1721.1/110047 https://orcid.org/0000-0001-9342-0191 https://orcid.org/0000-0001-9028-6708 |
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| author | Mar, Brendan D. Martinez, Todd J. Kulik, Heather Janine Seelam, Natasha |
| author2 | Massachusetts Institute of Technology. Department of Chemical Engineering |
| author_facet | Massachusetts Institute of Technology. Department of Chemical Engineering Mar, Brendan D. Martinez, Todd J. Kulik, Heather Janine Seelam, Natasha |
| author_sort | Mar, Brendan D. |
| collection | MIT |
| description | Recent algorithmic and hardware advances have enabled the application of electronic structure methods to the study of large-scale systems such as proteins with O(103) atoms. Most such methods benefit greatly from the use of reduced basis sets to further enhance their speed, but truly minimal basis sets are well-known to suffer from incompleteness error that gives rise to incorrect descriptions of chemical bonding, preventing minimal basis set use in production calculations. We present a strategy for improving these well-known shortcomings in minimal basis sets by selectively tuning the energetics and bonding of nitrogen and oxygen atoms within proteins and small molecules to reproduce polarized double-ζ basis set geometries at minimal basis set cost. We borrow the well-known +U correction from the density functional theory community normally employed for self-interaction errors and demonstrate its power in the context of correcting basis set incompleteness within a formally self-interaction-free Hartree–Fock framework. We tune the Hubbard U parameters for nitrogen and oxygen atoms on small-molecule tautomers (e.g., cytosine), demonstrate the applicability of the approach on a number of amide-containing molecules (e.g., formamide, alanine tripeptide), and test our strategy on a 10 protein test set where anomalous proton transfer events are reduced by 90% from RHF/STO-3G to RHF/STO-3G+U, bringing the latter into quantitative agreement with RHF/6-31G* results. Although developed with the study of biological molecules in mind, this empirically tuned U approach shows promise as an alternative strategy for correction of basis set incompleteness errors. |
| first_indexed | 2024-09-23T14:31:56Z |
| format | Article |
| id | mit-1721.1/110047 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:31:56Z |
| publishDate | 2017 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/1100472022-09-29T09:46:41Z Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness Mar, Brendan D. Martinez, Todd J. Kulik, Heather Janine Seelam, Natasha Massachusetts Institute of Technology. Department of Chemical Engineering Kulik, Heather J Kulik, Heather Janine Seelam, Natasha Recent algorithmic and hardware advances have enabled the application of electronic structure methods to the study of large-scale systems such as proteins with O(103) atoms. Most such methods benefit greatly from the use of reduced basis sets to further enhance their speed, but truly minimal basis sets are well-known to suffer from incompleteness error that gives rise to incorrect descriptions of chemical bonding, preventing minimal basis set use in production calculations. We present a strategy for improving these well-known shortcomings in minimal basis sets by selectively tuning the energetics and bonding of nitrogen and oxygen atoms within proteins and small molecules to reproduce polarized double-ζ basis set geometries at minimal basis set cost. We borrow the well-known +U correction from the density functional theory community normally employed for self-interaction errors and demonstrate its power in the context of correcting basis set incompleteness within a formally self-interaction-free Hartree–Fock framework. We tune the Hubbard U parameters for nitrogen and oxygen atoms on small-molecule tautomers (e.g., cytosine), demonstrate the applicability of the approach on a number of amide-containing molecules (e.g., formamide, alanine tripeptide), and test our strategy on a 10 protein test set where anomalous proton transfer events are reduced by 90% from RHF/STO-3G to RHF/STO-3G+U, bringing the latter into quantitative agreement with RHF/6-31G* results. Although developed with the study of biological molecules in mind, this empirically tuned U approach shows promise as an alternative strategy for correction of basis set incompleteness errors. United States. Office of the Director of Defense Research and Engineering (National Security Science and Engineering Faculty Fellowship) Burroughs Wellcome Fund. Career Award at the Scientific Interface 2017-06-20T14:17:18Z 2017-06-20T14:17:18Z 2016-07 Article http://purl.org/eprint/type/JournalArticle 1089-5639 1520-5215 http://hdl.handle.net/1721.1/110047 Kulik, Heather J., Natasha Seelam, Brendan D. Mar, and Todd J. Martínez. “Adapting DFT+Ufor the Chemically Motivated Correction of Minimal Basis Set Incompleteness.” The Journal of Physical Chemistry A 120, no. 29 (July 28, 2016): 5939–5949. https://orcid.org/0000-0001-9342-0191 https://orcid.org/0000-0001-9028-6708 en_US http://dx.doi.org/10.1021/acs.jpca.6b04527 The Journal of Physical Chemistry A Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society Prof. Kulik |
| spellingShingle | Mar, Brendan D. Martinez, Todd J. Kulik, Heather Janine Seelam, Natasha Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title | Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title_full | Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title_fullStr | Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title_full_unstemmed | Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title_short | Adapting DFT+U for the Chemically Motivated Correction of Minimal Basis Set Incompleteness |
| title_sort | adapting dft u for the chemically motivated correction of minimal basis set incompleteness |
| url | http://hdl.handle.net/1721.1/110047 https://orcid.org/0000-0001-9342-0191 https://orcid.org/0000-0001-9028-6708 |
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