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Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs

[Image: see text] Despite the inherently quantum mechanical nature of hydrogen bonding, it is unclear how nuclear quantum effects (NQEs) alter the strengths of hydrogen bonds. With this in mind, we use ab initio path integral molecular dynamics to determine the absolute contribution of NQEs to the b...

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Autores principales: Fang, Wei, Chen, Ji, Rossi, Mariana, Feng, Yexin, Li, Xin-Zheng, Michaelides, Angelos
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2016
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4933496/
https://www.ncbi.nlm.nih.gov/pubmed/27195654
http://dx.doi.org/10.1021/acs.jpclett.6b00777
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author Fang, Wei
Chen, Ji
Rossi, Mariana
Feng, Yexin
Li, Xin-Zheng
Michaelides, Angelos
author_facet Fang, Wei
Chen, Ji
Rossi, Mariana
Feng, Yexin
Li, Xin-Zheng
Michaelides, Angelos
author_sort Fang, Wei
collection PubMed
description [Image: see text] Despite the inherently quantum mechanical nature of hydrogen bonding, it is unclear how nuclear quantum effects (NQEs) alter the strengths of hydrogen bonds. With this in mind, we use ab initio path integral molecular dynamics to determine the absolute contribution of NQEs to the binding in DNA base pair complexes, arguably the most important hydrogen-bonded systems of all. We find that depending on the temperature, NQEs can either strengthen or weaken the binding within the hydrogen-bonded complexes. As a somewhat counterintuitive consequence, NQEs can have a smaller impact on hydrogen bond strengths at cryogenic temperatures than at room temperature. We rationalize this in terms of a competition of NQEs between low-frequency and high-frequency vibrational modes. Extending this idea, we also propose a simple model to predict the temperature dependence of NQEs on hydrogen bond strengths in general.
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spelling pubmed-49334962016-07-07 Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs Fang, Wei Chen, Ji Rossi, Mariana Feng, Yexin Li, Xin-Zheng Michaelides, Angelos J Phys Chem Lett [Image: see text] Despite the inherently quantum mechanical nature of hydrogen bonding, it is unclear how nuclear quantum effects (NQEs) alter the strengths of hydrogen bonds. With this in mind, we use ab initio path integral molecular dynamics to determine the absolute contribution of NQEs to the binding in DNA base pair complexes, arguably the most important hydrogen-bonded systems of all. We find that depending on the temperature, NQEs can either strengthen or weaken the binding within the hydrogen-bonded complexes. As a somewhat counterintuitive consequence, NQEs can have a smaller impact on hydrogen bond strengths at cryogenic temperatures than at room temperature. We rationalize this in terms of a competition of NQEs between low-frequency and high-frequency vibrational modes. Extending this idea, we also propose a simple model to predict the temperature dependence of NQEs on hydrogen bond strengths in general. American Chemical Society 2016-05-19 2016-06-02 /pmc/articles/PMC4933496/ /pubmed/27195654 http://dx.doi.org/10.1021/acs.jpclett.6b00777 Text en Copyright © 2016 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Fang, Wei
Chen, Ji
Rossi, Mariana
Feng, Yexin
Li, Xin-Zheng
Michaelides, Angelos
Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title_full Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title_fullStr Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title_full_unstemmed Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title_short Inverse Temperature Dependence of Nuclear Quantum Effects in DNA Base Pairs
title_sort inverse temperature dependence of nuclear quantum effects in dna base pairs
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4933496/
https://www.ncbi.nlm.nih.gov/pubmed/27195654
http://dx.doi.org/10.1021/acs.jpclett.6b00777
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