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Electron/Hole Mobilities of Periodic DNA and Nucleobase Structures from Large-Scale DFT Calculations
[Image: see text] Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functiona...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10331729/ https://www.ncbi.nlm.nih.gov/pubmed/37349270 http://dx.doi.org/10.1021/acs.jpcb.2c09141 |
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author | Kwon, Hyuna Kumar, Anshuman Del Ben, Mauro Wong, Bryan M. |
author_facet | Kwon, Hyuna Kumar, Anshuman Del Ben, Mauro Wong, Bryan M. |
author_sort | Kwon, Hyuna |
collection | PubMed |
description | [Image: see text] Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functional theory (DFT) calculations (up to 650 atoms) to systematically analyze the structural and electron/hole transport properties of fully periodic single- and double-stranded DNA. We examined the performance of various exchange–correlation functionals (LDA, BLYP, B3LYP, and B3LYP-D) and found that single-stranded thymine (T) and cytosine (C) are predominantly hole conductors, whereas single-stranded adenine (A) and guanine (G) are better electron conductors. For double-stranded DNA structures, the periodic A-T and G-C electronic band structures undergo a significant renormalization, which causes hole transport to only occur on the A and G nucleobases. Our calculations (1) provide new benchmarks for periodic nucleobase structures using dispersion-corrected hybrid functionals with large basis sets and (2) highlight the importance of dispersion effects for obtaining accurate geometries and electron/hole mobilities in these extended systems. |
format | Online Article Text |
id | pubmed-10331729 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-103317292023-07-11 Electron/Hole Mobilities of Periodic DNA and Nucleobase Structures from Large-Scale DFT Calculations Kwon, Hyuna Kumar, Anshuman Del Ben, Mauro Wong, Bryan M. J Phys Chem B [Image: see text] Electron/hole transfer mechanisms in DNA and polynucleotide structures continue to garner considerable interest as emerging charge-transport systems and molecular electronics. To shed mechanistic insight into these electronic properties, we carried out large-scale density functional theory (DFT) calculations (up to 650 atoms) to systematically analyze the structural and electron/hole transport properties of fully periodic single- and double-stranded DNA. We examined the performance of various exchange–correlation functionals (LDA, BLYP, B3LYP, and B3LYP-D) and found that single-stranded thymine (T) and cytosine (C) are predominantly hole conductors, whereas single-stranded adenine (A) and guanine (G) are better electron conductors. For double-stranded DNA structures, the periodic A-T and G-C electronic band structures undergo a significant renormalization, which causes hole transport to only occur on the A and G nucleobases. Our calculations (1) provide new benchmarks for periodic nucleobase structures using dispersion-corrected hybrid functionals with large basis sets and (2) highlight the importance of dispersion effects for obtaining accurate geometries and electron/hole mobilities in these extended systems. American Chemical Society 2023-06-22 /pmc/articles/PMC10331729/ /pubmed/37349270 http://dx.doi.org/10.1021/acs.jpcb.2c09141 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). |
spellingShingle | Kwon, Hyuna Kumar, Anshuman Del Ben, Mauro Wong, Bryan M. Electron/Hole Mobilities of Periodic DNA and Nucleobase Structures from Large-Scale DFT Calculations |
title | Electron/Hole Mobilities
of Periodic DNA and Nucleobase
Structures from Large-Scale DFT Calculations |
title_full | Electron/Hole Mobilities
of Periodic DNA and Nucleobase
Structures from Large-Scale DFT Calculations |
title_fullStr | Electron/Hole Mobilities
of Periodic DNA and Nucleobase
Structures from Large-Scale DFT Calculations |
title_full_unstemmed | Electron/Hole Mobilities
of Periodic DNA and Nucleobase
Structures from Large-Scale DFT Calculations |
title_short | Electron/Hole Mobilities
of Periodic DNA and Nucleobase
Structures from Large-Scale DFT Calculations |
title_sort | electron/hole mobilities
of periodic dna and nucleobase
structures from large-scale dft calculations |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10331729/ https://www.ncbi.nlm.nih.gov/pubmed/37349270 http://dx.doi.org/10.1021/acs.jpcb.2c09141 |
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